JP2019518602A5 - - Google Patents
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- JP2019518602A5 JP2019518602A5 JP2019516072A JP2019516072A JP2019518602A5 JP 2019518602 A5 JP2019518602 A5 JP 2019518602A5 JP 2019516072 A JP2019516072 A JP 2019516072A JP 2019516072 A JP2019516072 A JP 2019516072A JP 2019518602 A5 JP2019518602 A5 JP 2019518602A5
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 54
- 150000001875 compounds Chemical class 0.000 claims description 40
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 28
- 229910052717 sulfur Inorganic materials 0.000 claims description 28
- 239000011593 sulfur Substances 0.000 claims description 28
- 239000000047 product Substances 0.000 claims description 27
- 229910052726 zirconium Inorganic materials 0.000 claims description 27
- 239000003513 alkali Substances 0.000 claims description 21
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 21
- 229910052782 aluminium Inorganic materials 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 9
- 239000003381 stabilizer Substances 0.000 claims description 9
- 230000003197 catalytic Effects 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 8
- 150000004679 hydroxides Chemical class 0.000 claims description 7
- 239000000969 carrier Substances 0.000 claims description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N precursor Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- LLZRNZOLAXHGLL-UHFFFAOYSA-J Titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims description 5
- 150000003609 titanium compounds Chemical class 0.000 claims description 5
- XNGIFLGASWRNHJ-UHFFFAOYSA-N Phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 3
- 102000014961 Protein Precursors Human genes 0.000 claims description 3
- 108010078762 Protein Precursors Proteins 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 230000001699 photocatalysis Effects 0.000 claims description 3
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxyl anion Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 238000010335 hydrothermal treatment Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 16
- 238000007171 acid catalysis Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- -1 sulfuric acid Chemical class 0.000 description 1
Description
したがって、本発明は以下の範囲に及ぶ：
− Ｓｉ、Ａｌ及びＺｒの酸化物から選択される少なくとも１つの化合物の含有量が、酸化物として計算して酸化物の総重量の２〜５０重量％、好ましくは２〜３０重量％の量であり、硫黄含有量が、酸化物の総重量に対して１５０ｐｐｍ未満、好ましくは１００ｐｐｍ未満、より好ましくは８０ｐｐｍ未満である、アナターゼ二酸化チタン；
− Ｓｉ、Ａｌ及びＺｒの酸化物から選択される少なくとも１つの化合物の含有量が、酸化物として計算して酸化物の総重量の３〜２０重量％、より好ましくは４〜１２重量％の量であり、硫黄含有量が、酸化物の総重量に対して１５０ｐｐｍ未満、好ましくは１００ｐｐｍ未満、より好ましくは８０ｐｐｍ未満である、アナターゼ二酸化チタン；
− ＳｉＯ２の含有量が、酸化物として計算して酸化物の総重量の２〜３０重量％、好ましくは３〜２０重量％、より好ましくは４〜１２重量％の量であり、硫黄含有量が、酸化物の総重量に対して１００ｐｐｍ未満、好ましくは８０ｐｐｍ未満である、アナターゼ二酸化チタン；
並びに：
− Ｓｉ、Ａｌ及びＺｒの酸化物から選択される少なくとも１つの化合物の含有量が、酸化物として計算して酸化物の総重量の２〜５０重量％、好ましくは２〜３０重量％、より好ましくは３〜２０重量％、最も好ましくは４〜１２重量％の量であり、硫黄含有量が、酸化物の総重量に対して１５０ｐｐｍ未満、好ましくは１００ｐｐｍ未満、より好ましくは８０ｐｐｍ未満である、本発明のアナターゼ二酸化チタンを調製する方法であって、この方法では
メタチタン酸又は硫酸チタニルから選択されるチタン化合物を、Ｓｉ、Ａｌ及びＺｒの酸化物及び／若しくは水酸化物から選択される少なくとも１つの化合物、又はそれらの前駆体と、水性媒体中で混合し、
Ｓｉ、Ａｌ及びＺｒの酸化物及び／又は水酸化物から選択される少なくとも１つの化合物を析出させ、
酸化物の総重量に対して、アルカリ含有量が２００ｐｐｍを超える場合、得られた生成物を処理してそのアルカリ含有量を最大で２００ｐｐｍのレベルまで低下させ、
生成物を任意選択でろ過し、任意選択で水で洗浄し、任意選択で乾燥させ、
次いで、５００℃超、好ましくは８００℃〜１２００℃の範囲の温度で、硫酸などの残留硫黄含有化合物を、酸化物の総重量に対して１５０ｐｐｍ未満、好ましくは１００ｐｐｍ未満、より好ましくは８０ｐｐｍ未満のレベルまで分解するのに十分な時間をかけて、好ましくは０．５〜１２時間の時間をかけて、生成物をか焼処理に付す。
− メタチタン酸をＳｉＯ２前駆体化合物と混合し、Ｓｉの酸化物及び／又は水酸化物の少なくとも１つを析出させ、酸化物の総重量に対して、アルカリ含有量が２００ｐｐｍを超える場合、得られた生成物を処理してそのアルカリ含有量を最大で２００ｐｐｍのレベルまで低下させ、得られた生成物を任意選択でろ過し任意選択で洗浄し、得られた生成物を任意選択で乾燥させ、５００℃超、好ましくは８００℃〜１２００℃の範囲の温度で、硫酸などの残留硫黄含有化合物を酸化物の総重量に対して１００ｐｐｍ未満、好ましくは８０ｐｐｍ未満のレベルまで分解するのに十分な時間をかけて、好ましくは０．５〜１２時間の時間をかけて、生成物をか焼処理に付す、本発明のアナターゼ二酸化チタンの実施形態を調製する方法、
− ＴｉＯ２ゾルから選択されるチタン化合物をＳｉＯ２ゾルと混合し、析出物が得られるようにｐＨを調整し、酸化物の総重量に対して、アルカリ含有量が２００ｐｐｍを超える場合、得られた析出物を処理してアルカリ含有量を最大で２００ｐｐｍのレベルまで低下させ、得られた生成物を任意選択でろ過し、任意選択で洗浄し、任意選択で乾燥させ、５００℃超、好ましくは８００℃〜１２００℃の範囲の温度で、硫酸などの残留硫黄含有化合物を酸化物の総重量に対して１５０ｐｐｍ未満、好ましくは１００ｐｐｍ未満、より好ましくは８０ｐｐｍ未満のレベルまで分解するのに十分な時間をかけて、好ましくは８００℃〜１２００℃の範囲の温度で、好ましくは０．５〜１２時間の時間をかけて、得られた生成物をか焼処理に付す、アナターゼ二酸化チタンを調製する方法、
− ある含有量の安定化剤を有するアナターゼチタニアを、５００℃超、好ましくは８００〜１２００℃の範囲の温度で、硫酸などの残留硫黄含有化合物を酸化物の総重量に対して１５０ｐｐｍ未満、好ましくは１００ｐｐｍ未満、より好ましくは８０ｐｐｍ未満のレベルまで分解するのに十分な時間をかけて、好ましくは少なくとも３０分の時間をかけて処理し、安定化剤が、Ｓｉ、Ａｌ及びＺｒの酸化物から選択され、安定化剤の含有量が、酸化物として計算して酸化物の総重量の２〜５０重量％、好ましくは２〜３０重量％の範囲である、安定化アナターゼチタニアの硫黄含有量を低下させる方法、
− Ｓｉ、Ａｌ及びＺｒの酸化物から選択される少なくとも１つの化合物の含有量が、酸化物として計算して酸化物の総重量の２〜５０重量％、好ましくは２〜３０重量％の量である安定化アナターゼチタニアの硫黄含有量を、酸化物の総重量に対して１５０ｐｐｍ未満、好ましくは１００ｐｐｍ未満、より好ましくは８０ｐｐｍ未満のレベルまで低下させるための、５００℃を超える温度でのか焼処理の使用。
− 触媒反応、ガス・ツー・リキッド反応（ｇａｓ−ｔｏ−ｌｉｑｕｉｄ ｒｅａｃｔｉｏｎｓ）、例えば特にフィッシャー・トロプシュ触媒作用、選択的触媒還元（ＳＣＲ）、酸化触媒作用、光触媒作用、水素化処理触媒作用、クラウス触媒作用、フタル酸触媒作用における触媒又は触媒担体としての、本発明の方法に従って得られる本発明のアナターゼ二酸化チタンの使用。
− 本発明の方法に従って得られる本発明のアナターゼ二酸化チタンを含む、触媒又は触媒担体。
Therefore, the present invention extends to the following scope:
-The content of at least one compound selected from the oxides of Si, Al and Zr is calculated as an oxide in an amount of 2 to 50% by weight, preferably 2 to 30% by weight of the total weight of the oxide. Anatase titanium dioxide, which has a sulfur content of less than 150 ppm, preferably less than 100 ppm, more preferably less than 80 ppm, based on the total weight of the oxide;
-The content of at least one compound selected from the oxides of Si, Al and Zr is calculated as an oxide in an amount of 3 to 20% by weight, more preferably 4 to 12% by weight of the total weight of the oxide. Anatase titanium dioxide, wherein the sulfur content is less than 150 ppm, preferably less than 100 ppm, more preferably less than 80 ppm, based on the total weight of the oxide;
− The content of SiO 2 is 2 to 30% by weight, preferably 3 to 20% by weight, more preferably 4 to 12% by weight, and the sulfur content, calculated as an oxide. However, less than 100 ppm, preferably less than 80 ppm, based on the total weight of the oxide, anatase titanium dioxide;
and:
-The content of at least one compound selected from the oxides of Si, Al and Zr is calculated as an oxide to be 2 to 50% by weight, preferably 2 to 30% by weight, more preferably the total weight of the oxide. Is an amount of 3 to 20% by weight, most preferably 4 to 12% by weight, and the sulfur content is less than 150 ppm, preferably less than 100 ppm, more preferably less than 80 ppm, based on the total weight of the oxide. The method for preparing anatase titanium dioxide of the present invention, wherein the titanium compound selected from metatitanic acid or titanyl sulfate is at least one selected from oxides and / or hydroxides of Si, Al and Zr. Mix with compounds or their precursors in an aqueous medium and
Precipitate at least one compound selected from oxides and / or hydroxides of Si, Al and Zr.
If the alkali content exceeds 200 ppm with respect to the total weight of the oxide, the resulting product is treated to reduce its alkali content to a level of up to 200 ppm.
The product is optionally filtered, optionally washed with water, optionally dried,
Then, at a temperature above 500 ° C., preferably in the range of 800 ° C. to 1200 ° C., the residual sulfur-containing compound such as sulfuric acid was added to the total weight of the oxide in an amount of less than 150 ppm, preferably less than 100 ppm, more preferably less than 80 ppm. The product is subjected to calcination, taking a sufficient amount of time to decompose to the level, preferably 0.5-12 hours.
− Metatitanic acid is mixed with the SiO 2 precursor compound to precipitate at least one of the oxides and / or hydroxides of Si, which is obtained when the alkali content exceeds 200 ppm with respect to the total weight of the oxide. The resulting product is treated to reduce its alkali content to a level of up to 200 ppm, the resulting product is optionally filtered and optionally washed, and the resulting product is optionally dried. Sufficient to decompose residual alkali-containing compounds such as sulfuric acid to a level of less than 100 ppm, preferably less than 80 ppm, based on the total weight of the oxide, at temperatures above 500 ° C., preferably in the range of 800 ° C. to 1200 ° C. A method of preparing an embodiment of the anatase titanium dioxide of the present invention, wherein the product is subjected to a calcination treatment over time, preferably over a period of 0.5-12 hours.
− A titanium compound selected from the TiO 2 sol is mixed with the SiO 2 sol and the pH is adjusted to give a precipitate, which is obtained when the alkali content exceeds 200 ppm with respect to the total weight of the oxide. The precipitate was treated to reduce the alkali content to a level of up to 200 ppm and the resulting product was optionally filtered, optionally washed, optionally dried and above 500 ° C., preferably above 500 ° C. Sufficient time to decompose a residual sulfur-containing compound such as sulfuric acid to a level of less than 150 ppm, preferably less than 100 ppm, more preferably less than 80 ppm based on the total weight of the oxide at a temperature in the range of 800 ° C to 1200 ° C. A method for preparing anatase titanium dioxide, which comprises subjecting the obtained product to a calcination treatment at a temperature in the range of 800 ° C. to 1200 ° C., preferably over a time of 0.5 to 12 hours. ,
− Anatase titania with a certain content of stabilizer at temperatures above 500 ° C, preferably in the range 800-1200 ° C, with residual sulfur-containing compounds such as sulfuric acid, preferably less than 150 ppm based on the total weight of the oxide. Is treated over a time sufficient to decompose to a level of less than 100 ppm, more preferably less than 80 ppm, preferably at least 30 minutes, and the stabilizer is from the oxides of Si, Al and Zr. The sulfur content of the stabilized anatase titania, which is selected and the stabilizer content is in the range of 2-50% by weight, preferably 2-30% by weight of the total weight of the oxide calculated as an oxide. How to lower,
-The content of at least one compound selected from the oxides of Si, Al and Zr is calculated as an oxide in an amount of 2 to 50% by weight, preferably 2 to 30% by weight of the total weight of the oxide. A roasting treatment at a temperature above 500 ° C. to reduce the sulfur content of a stabilized anatase titania to a level of less than 150 ppm, preferably less than 100 ppm, more preferably less than 80 ppm based on the total weight of the oxide. use.
-Catalyst, gas-to-liquid reactions, such as Fisher-Tropsch catalysis, selective catalytic reduction (SCR), oxidation catalysis, photocatalysis, hydrothermalization catalysis, Claus catalyst Use of the anatase titanium dioxide of the present invention obtained according to the method of the present invention as a catalyst or catalyst carrier in action, phthalic acid catalysis.
-A catalyst or catalyst carrier containing the anatase titanium dioxide of the present invention obtained according to the method of the present invention.
本発明による例及び比較例並びに触媒試験の上記の結果は、本発明の材料の特性の組み合わせ、すなわち、高い比表面積、アナターゼ含有量及び低い硫黄含有量が、そのより優れた触媒特性をもたらすことを示している。
なお、本願は、特許請求の範囲に記載の発明に関するものであるが、他の態様として以下も包含し得る。
１．Ｓｉ、Ａｌ及びＺｒの酸化物から選択される少なくとも１つの化合物の含有量が、酸化物として計算して酸化物の総重量の２〜５０重量％、好ましくは２〜３０重量％の量であり、硫黄含有量が、酸化物の総重量に対して１５０ｐｐｍ未満、好ましくは１００ｐｐｍ未満、より好ましくは８０ｐｐｍ未満である、アナターゼ二酸化チタン。
２．Ｓｉ、Ａｌ及びＺｒの酸化物から選択される少なくとも１つの化合物の含有量が、酸化物として計算して酸化物の総重量の３〜２０重量％、好ましくは４〜１２重量％の量であり、硫黄含有量が、酸化物の総重量に対して１５０ｐｐｍ未満、好ましくは１００ｐｐｍ未満、より好ましくは８０ｐｐｍ未満である、上記１に記載のアナターゼ二酸化チタン。
３．ＳｉＯ ２ の含有量が、酸化物として計算して酸化物の総重量の２〜３０重量％、好ましくは３〜２０重量％、より好ましくは４〜１２重量％の量であり、硫黄含有量が、酸化物の総重量に対して１００ｐｐｍ未満、好ましくは８０ｐｐｍ未満である、上記１に記載のアナターゼ二酸化チタン。
４．Ｓｉ、Ａｌ及びＺｒの酸化物から選択される少なくとも１つの化合物の含有量が、酸化物として計算して酸化物の総重量の２〜５０重量％、好ましくは２〜３０重量％、より好ましくは３〜２０重量％．最も好ましくは４〜１２重量％の量であり、硫黄含有量が、酸化物の総重量に対して１５０ｐｐｍ未満、好ましくは１００ｐｐｍ未満、より好ましくは８０ｐｐｍ未満である、上記１に記載のアナターゼ二酸化チタンを調製する方法であって、
− メタチタン酸又は硫酸チタニルから選択されるチタン化合物を、Ｓｉ、Ａｌ及びＺｒの酸化物及び／若しくは水酸化物から選択される少なくとも１つの化合物、又はそれらの前駆体と、水性媒体中で混合し、
− Ｓｉ、Ａｌ及びＺｒの酸化物及び／又は水酸化物から選択される少なくとも１つの化合物を析出させ、
− 酸化物の総重量に対して、アルカリ含有量が２００ｐｐｍを超える場合、得られた生成物を処理してアルカリ含有量を最大で２００ｐｐｍのレベルまで低下させ、
− 生成物を任意選択でろ過し、任意選択で水で洗浄し、任意選択で乾燥させ、
− 次いで、５００℃超、好ましくは８００℃〜１２００℃の範囲の温度で、硫酸などの残留硫黄含有化合物を、酸化物の総重量に対して１５０ｐｐｍ未満、好ましくは１００ｐｐｍ未満、より好ましくは８０ｐｐｍ未満のレベルまで分解するのに十分な時間をかけて、好ましくは０．５〜１２時間の時間をかけて、生成物をか焼処理に付す、
方法。
５．メタチタン酸をＳｉＯ ２ 前駆体化合物と混合し、Ｓｉの少なくとも１つの酸化物及び／又は水酸化物を析出させ、酸化物の総重量に対して、アルカリ含有量が２００ｐｐｍを超える場合、得られた生成物を処理してアルカリ含有量を最大で２００ｐｐｍのレベルまで低下させ、得られた生成物を任意選択でろ過し任意選択で洗浄し、得られた生成物を任意選択で乾燥させ、次いで、５００℃超、好ましくは８００℃〜１２００℃の範囲の温度で、硫酸などの残留硫黄含有化合物を酸化物の総重量に対して１００ｐｐｍ未満、好ましくは８０ｐｐｍ未満のレベルまで分解するのに十分な時間をかけて、好ましくは０．５〜１２時間の時間をかけて、生成物をか焼処理に付す、上記３に記載のアナターゼ二酸化チタンを調製する方法。
６．ＴｉＯ ２ ゾルから選択されるチタン化合物をＳｉＯ ２ ゾルと混合し、析出物を得るためにｐＨを調整し、酸化物の総重量に対して、アルカリ含有量が２００ｐｐｍを超える場合、得られた析出物を処理してアルカリ含有量を酸化物の総重量に対して最大で２００ｐｐｍのレベルまで低下させ、得られた生成物を任意選択でろ過し、任意選択で洗浄し、任意選択で乾燥させ、５００℃超、好ましくは８００℃〜１２００℃の範囲の温度で、硫酸などの残留硫黄含有化合物を酸化物の総重量に対して１５０ｐｐｍ未満、好ましくは１００ｐｐｍ未満、より好ましくは８０ｐｐｍ未満のレベルまで分解するのに十分な時間をかけて、好ましくは８００℃〜１２００℃の範囲の温度で、好ましくは０．５〜１２時間の時間をかけて、得られた生成物をか焼処理に付す、上記３に記載のアナターゼ二酸化チタンを調製する方法。
７．安定化剤を含有するアナターゼチタニアを、５００℃超、好ましくは８００〜１２００℃の範囲の温度で、硫酸などの残留硫黄含有化合物を酸化物の総重量に対して１５０ｐｐｍ未満、好ましくは１００ｐｐｍ未満、より好ましくは８０ｐｐｍ未満のレベルまで分解するのに十分な時間をかけて、好ましくは少なくとも３０分の時間をかけて処理し、安定化剤が、Ｓｉ、Ａｌ及びＺｒの酸化物から選択され、安定化剤の含有量が、酸化物として計算して酸化物の総重量の２〜５０重量％、好ましくは２〜３０重量％の範囲である、安定化アナターゼチタニアの硫黄含有量を低下させる方法。
８．安定化アナターゼチタニアの硫黄含有量を、酸化物の総重量に対して１５０ｐｐｍ未満、好ましくは１００ｐｐｍ未満、より好ましくは８０ｐｐｍ未満のレベルまで低下させるための、５００℃を超える温度でのか焼処理の使用。
９．触媒反応、ガス・ツー・リキッド反応、例えば特にフィッシャー・トロプシュ触媒作用、選択的触媒還元（ＳＣＲ）、酸化触媒作用、光触媒作用、水素化処理触媒作用、クラウス触媒作用、フタル酸触媒作用における、触媒又は触媒担体としての、上記１〜３のいずれか一つに記載の又は上記４〜７のいずれか一つに記載の方法に従って得られるアナターゼ二酸化チタンの使用。
１０．上記１〜３のいずれか一つに記載の又は上記４〜７のいずれか一つに記載の方法に従って得られるアナターゼ二酸化チタンを含む、触媒又は触媒担体。
The above examples and comparative examples according to the present invention and the above results of the catalyst test show that a combination of the properties of the materials of the present invention, that is, high specific surface area, anatase content and low sulfur content, results in better catalytic properties. Is shown.
Although the present application relates to the invention described in the claims, the following may be included as other aspects.
1. 1. The content of at least one compound selected from the oxides of Si, Al and Zr is 2 to 50% by weight, preferably 2 to 30% by weight, of the total weight of the oxide calculated as the oxide. Anatase titanium dioxide having a sulfur content of less than 150 ppm, preferably less than 100 ppm, more preferably less than 80 ppm, based on the total weight of the oxide.
2. The content of at least one compound selected from the oxides of Si, Al and Zr is 3 to 20% by weight, preferably 4 to 12% by weight, of the total weight of the oxide calculated as the oxide. The anatase titanium dioxide according to 1 above, wherein the sulfur content is less than 150 ppm, preferably less than 100 ppm, more preferably less than 80 ppm based on the total weight of the oxide.
3. 3. The content of SiO 2 is 2 to 30% by weight, preferably 3 to 20% by weight, more preferably 4 to 12% by weight of the total weight of the oxide calculated as an oxide, and the sulfur content is high. The anatase titanium dioxide according to 1 above, which is less than 100 ppm, preferably less than 80 ppm, based on the total weight of the oxide.
4. The content of at least one compound selected from the oxides of Si, Al and Zr is calculated as an oxide to be 2 to 50% by weight, preferably 2 to 30% by weight, more preferably the total weight of the oxide. 3 to 20% by weight. The anatase titanium dioxide according to 1 above, wherein the amount is most preferably 4 to 12% by weight, and the sulfur content is less than 150 ppm, preferably less than 100 ppm, more preferably less than 80 ppm based on the total weight of the oxide. Is a method of preparing
-Titanium compounds selected from metatitanic acid or titanyl sulfate are mixed in an aqueous medium with at least one compound selected from oxides and / or hydroxides of Si, Al and Zr, or precursors thereof. ,
-Precipitate at least one compound selected from oxides and / or hydroxides of Si, Al and Zr.
-If the alkali content exceeds 200 ppm with respect to the total weight of the oxide, the resulting product is treated to reduce the alkali content to a level of up to 200 ppm.
− The product is optionally filtered, optionally washed with water, optionally dried and optionally dried.
-Then, at a temperature above 500 ° C., preferably in the range of 800 ° C. to 1200 ° C., the residual sulfur-containing compound such as sulfuric acid was added to less than 150 ppm, preferably less than 100 ppm, more preferably less than 80 ppm based on the total weight of the oxide. The product is subjected to calcination, taking a sufficient amount of time to decompose to the level of, preferably 0.5-12 hours.
Method.
5. Metatitanic acid was mixed with the SiO 2 precursor compound to precipitate at least one oxide and / or hydroxide of Si, which was obtained when the alkali content exceeded 200 ppm with respect to the total weight of the oxide. The product is treated to reduce the alkali content to a level of up to 200 ppm, the resulting product is optionally filtered and optionally washed, the resulting product is optionally dried and then optionally dried. Sufficient time to decompose residual alkali-containing compounds such as sulfuric acid to a level of less than 100 ppm, preferably less than 80 ppm, based on the total weight of the oxide, at temperatures above 500 ° C., preferably in the range of 800 ° C. to 1200 ° C. The method for preparing the anatase titanium dioxide according to 3 above, wherein the product is subjected to a calcination treatment, preferably over a period of 0.5 to 12 hours.
6. A titanium compound selected from the TiO 2 sol is mixed with the SiO 2 sol, the pH is adjusted to obtain a precipitate, and the resulting precipitate is obtained when the alkali content exceeds 200 ppm with respect to the total weight of the oxide. The compound is processed to reduce the alkali content to a level of up to 200 ppm with respect to the total weight of the oxide, the resulting product is optionally filtered, optionally washed and optionally dried. Decomposes residual alkali-containing compounds such as sulfuric acid to a level of less than 150 ppm, preferably less than 100 ppm, more preferably less than 80 ppm based on the total weight of the oxide at temperatures above 500 ° C., preferably in the range of 800 ° C. to 1200 ° C. The resulting product is subjected to a calcination treatment, preferably at a temperature in the range of 800 ° C. to 1200 ° C., preferably over a period of 0.5-12 hours. 3. The method for preparing anatase titanium dioxide according to 3.
7. Anatase titania containing a stabilizer at a temperature in the range of more than 500 ° C., preferably 800 ° C. to 1200 ° C., and a residual sulfur-containing compound such as sulfuric acid at less than 150 ppm, preferably less than 100 ppm, based on the total weight of the oxide. Treatment is more preferably carried out over a period of sufficient time to decompose to a level of less than 80 ppm, preferably at least 30 minutes, and the stabilizer is selected from oxides of Si, Al and Zr and is stable. A method for reducing the sulfur content of stabilized anatase titania, wherein the content of the agent is in the range of 2-50% by weight, preferably 2-30% by weight of the total weight of the oxide, calculated as an oxide.
8. Use of roasting at temperatures above 500 ° C. to reduce the sulfur content of stabilized anatase titania to levels below 150 ppm, preferably less than 100 ppm, more preferably less than 80 ppm relative to the total weight of the oxide. ..
9. Catalysis in catalytic reactions, gas-to-liquid reactions, such as Fisher-Tropsch catalysis, selective catalytic reduction (SCR), oxidation catalytic action, photocatalytic action, hydrogenation catalytic action, Claus catalysis, phthalic acid catalysis. Alternatively, use of anatase titanium dioxide obtained as a catalyst carrier according to the method according to any one of 1 to 3 above or 4 to 7 above.
10. A catalyst or catalyst carrier comprising anatase titanium dioxide obtained according to the method according to any one of 1 to 3 above or any one of 4 to 7 above.
Claims (11)
− メタチタン酸又は硫酸チタニルから選択されるチタン化合物を、Ｓｉ及びＺｒの酸化物及び／若しくは水酸化物から選択される少なくとも１つの化合物、またはＳｉ、Ａｌ及びＺｒの酸化物から選択される少なくとも２つの化合物、あるいはそれらの前駆体と、水性媒体中で混合し、
− Ｓｉ及びＺｒの酸化物及び／又は水酸化物から選択される少なくとも１つの化合物、またはＳｉ、Ａｌ及びＺｒの酸化物から選択される少なくとも２つの化合物を析出させ、
− 酸化物の総重量に対して、アルカリ含有量が２００ｐｐｍを超える場合、得られた生成物を処理してアルカリ含有量を最大で２００ｐｐｍのレベルまで低下させ、
− 生成物を任意選択でろ過し、任意選択で水で洗浄し、任意選択で乾燥させ、
− 次いで、５００℃超の温度で、残留硫黄含有化合物を酸化物の総重量に対して１５０ｐｐｍ未満のレベルまで分解するのに十分な時間をかけて、生成物をか焼処理に付す、
方法。 The content of at least one compound selected from the oxides of Si and Zr, or at least two compounds selected from the oxides of Si, Al and Zr, is calculated as the oxide and is the total weight of the oxide. 2-50 is the amount of weight%, a sulfur content of less than 150ppm based on the total weight of the oxides, a process for preparing anatase titanium dioxide according to claim 1,
-The titanium compound selected from metatitanic acid or titanyl sulfate is at least one compound selected from oxides and / or hydroxides of Si and Zr, or at least 2 selected from oxides of Si, Al and Zr. Mix with two compounds, or their precursors, in an aqueous medium and
-Precipitate at least one compound selected from oxides and / or hydroxides of Si and Zr, or at least two compounds selected from oxides of Si, Al and Zr .
-If the alkali content exceeds 200 ppm with respect to the total weight of the oxide, the resulting product is treated to reduce the alkali content to a level of up to 200 ppm.
− The product is optionally filtered, optionally washed with water, optionally dried and optionally dried.
- then, at 500 ° C. greater than the temperature, for a time sufficient to decompose to levels below 150ppm the residual sulfur-containing compounds based on the total weight of oxides, subjecting the product to calcination treatment,
Method.
安定化剤が、Ｓｉ及びＺｒの酸化物、またはＳｉ、Ａｌ及びＺｒの酸化物から選択される少なくとも２つの化合物から選択され、そして、安定化剤の含有量が、酸化物として計算して酸化物の総重量の２〜５０重量％の範囲である、前記使用。 The sulfur content of the stabilized anatase titania, for reducing to a level of less than 150ppm based on the total weight of the oxide to the use of calcination treatment at a temperature exceeding 500 ° C.,
The stabilizer is selected from at least two compounds selected from oxides of Si and Zr, or oxides of Si, Al and Zr, and the content of the stabilizer is calculated as oxide and oxidized. The use, which is in the range of 2-50% by weight of the total weight of the object.
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| US15/173,801 | 2016-06-06 | ||
| PCT/EP2017/063439 WO2017211710A1 (en) | 2016-06-06 | 2017-06-02 | Process for reducing the sulphur content of anatase titania and the so-obtained product |
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| US5169821A (en) * | 1991-11-14 | 1992-12-08 | Exxon Research And Engineering Company | Method for stabilizing titania supported cobalt catalyst and the catalyst for use in Fischer-Tropsch process |
| GB9213140D0 (en) * | 1992-06-20 | 1992-08-05 | Tioxide Specialties Ltd | Preparation of anatase titanium dioxide |
| US5362908A (en) * | 1993-03-10 | 1994-11-08 | Amoco Corporation | Catalyst and method for purifying crude terephthalic acid, isophthalic acid or naphthalene dicarboxylic acid |
| JP3643948B2 (en) * | 1999-03-15 | 2005-04-27 | 株式会社豊田中央研究所 | Titania-zirconia powder and method for producing the same |
| DE10333029A1 (en) | 2003-07-21 | 2005-02-17 | Merck Patent Gmbh | Nanoparticulate UV protectants used in cosmetic, sunscreen, dermatological or other protective uses (e.g. as textile or packaging coatings) comprise a metal oxide with a silicon dioxide coating |
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