JP2008081392A - Porous zirconia-based powder and its manufacture method - Google Patents
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000000843 powder Substances 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title abstract description 7
- 239000011148 porous material Substances 0.000 claims abstract description 64
- QRTRRDMHGTZPBF-UHFFFAOYSA-L oxygen(2-);zirconium(4+);sulfate Chemical compound [O-2].[Zr+4].[O-]S([O-])(=O)=O QRTRRDMHGTZPBF-UHFFFAOYSA-L 0.000 claims abstract description 32
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims description 35
- 230000001180 sulfating effect Effects 0.000 claims description 21
- 150000003754 zirconium Chemical class 0.000 claims description 18
- 239000012266 salt solution Substances 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 8
- 150000002910 rare earth metals Chemical class 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 229910052706 scandium Inorganic materials 0.000 claims description 7
- 229910052723 transition metal Inorganic materials 0.000 claims description 7
- 229910052727 yttrium Inorganic materials 0.000 claims description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- 229910052738 indium Inorganic materials 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000002002 slurry Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000006386 neutralization reaction Methods 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 230000019635 sulfation Effects 0.000 description 6
- 238000005670 sulfation reaction Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- -1 zirconium ions Chemical class 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- VZJJZMXEQNFTLL-UHFFFAOYSA-N chloro hypochlorite;zirconium;octahydrate Chemical compound O.O.O.O.O.O.O.O.[Zr].ClOCl VZJJZMXEQNFTLL-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 241000588731 Hafnia Species 0.000 description 1
- 241001178829 Konia Species 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical class ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
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- Y02T10/22—
Abstract
Description
本発明は、多孔質ジルコニア系粉末及びその製造方法に関する。 The present invention relates to a porous zirconia powder and a method for producing the same.
従来、触媒担体として用いられているジルコニア単体の４００℃における比表面積は、せいぜい１００ｍ２／ｇ程度である。また、それ以上の比表面積のジルコニア単体は、一般的には一定の構造を有しない非晶質である。このため、ジルコニア単体を触媒担体として用いる場合には、４００℃以上の高温では比表面積が小さくなる結果、高温下で安定した性能を得ることができない。従って、触媒担体として用いるためには、更なる耐熱性（熱安定性）の改善が必要である。 Conventionally, the specific surface area at 400 ° C. of zirconia alone used as a catalyst support is at most about 100 m 2 / g. Further, zirconia alone having a specific surface area larger than that is generally amorphous with no fixed structure. For this reason, when using a zirconia simple substance as a catalyst support | carrier, as a result of a specific surface area becoming small at high temperature of 400 degreeC or more, the performance stable at high temperature cannot be obtained. Therefore, in order to use it as a catalyst carrier, further improvement in heat resistance (thermal stability) is necessary.
これに対して、酸化ジルコニウムと酸化セリウムからなるジルコニア−セリア組成物は、１０００℃の高温においても比較的大きな比表面積を確保できる点でジルコニアと比べて耐熱性が高い。 In contrast, a zirconia-ceria composition composed of zirconium oxide and cerium oxide has higher heat resistance than zirconia in that a relatively large specific surface area can be secured even at a high temperature of 1000 ° C.
最近では、触媒担体の比表面積の耐熱性に加えて、細孔容積の耐熱性が求められている。触媒担体に活性種である貴金属（活性貴金属）を担持する場合には、貴金属は１０〜１００ｎｍの直径を有する細孔に分散性良く担持される。従って、高温でも１０〜１００ｎｍの直径を有する細孔の容積が大きいものが望ましい。即ち、直径が１０〜１００ｎｍの細孔の高温での耐熱性が求められている。 Recently, in addition to the heat resistance of the specific surface area of the catalyst carrier, the heat resistance of the pore volume is required. When a noble metal that is an active species (active noble metal) is supported on the catalyst support, the noble metal is supported with good dispersibility in pores having a diameter of 10 to 100 nm. Accordingly, it is desirable that the pore volume having a diameter of 10 to 100 nm is large even at a high temperature. That is, heat resistance at a high temperature of pores having a diameter of 10 to 100 nm is required.
特許文献１には、「約５００℃の空気中での２時間にわたる仮焼の後に、約０．８ｍｌ／ｇを上回る全気孔体積を有する酸化セリウム、酸化ジルコニウム、（Ｃｅ，Ｚｒ）Ｏ２複合酸化物、（Ｃｅ，Ｚｒ）Ｏ２固溶体」が記載されている。
In
特許文献２には、「少なくとも０．６ｃｍ３／ｇの全気孔容量を有し、しかも全気孔容量の少なくとも５０％が１０〜１００ｎｍの直径を有する気孔からなる、混合セリウム又はジルコニウム酸化物」が記載されている。また、その実施例では、８００℃で６時間焼成した後に、約０．８ｃｍ３／ｇの気孔容量を有する複合酸化物が記載されている。
しかしながら、自動車用触媒の実際の使用温度が１０００℃以上であることを考慮すると、上記２つの文献に記載された複合酸化物は、高温での耐熱性を十分有しているとは言い難い。 However, considering that the actual use temperature of the catalyst for automobiles is 1000 ° C. or higher, it is difficult to say that the composite oxides described in the above two documents have sufficient heat resistance at high temperatures.
他方、特許文献３には、ジルコニア系多孔質体及びその製造方法が記載されている。具体的には、「ＢＪＨ法に基づく細孔分布において、２０〜１１０ｎｍの気孔径にピークを有し、且つ、全気孔容量が０．４ｃｃ／ｇ以上で、１０〜１００ｎｍの直径を有する気孔の合計容積が全気孔容量の５０％以上を占めるジルコニア系多孔質体」が記載されている。
On the other hand,
また、製造方法としては、「ジルコニア系多孔質体を製造する方法であって、（１）８０℃以上９５℃未満の硫酸塩化剤（硫酸塩を生成させる試薬）と８０℃以上９５℃未満のジルコニウム塩溶液とを混合することにより調製された塩基性硫酸ジルコニウム含有反応液Ａと、６５℃以上８０℃未満の硫酸塩化剤と６５℃以上８０℃未満のジルコニウム塩溶液とを混合することにより調製された塩基性硫酸ジルコニウム含有反応液Ｂとを混合する第１工程、（２）第１工程で得られる反応液を９５℃以上で熟成する第２工程、（３）第２工程で得られる混合液にアルカリを添加して前記塩基性硫酸ジルコニウムを中和することにより、水酸化ジルコニウムを生成させる第３工程、及び（４）前記水酸化ジルコニウムを熱処理することにより、ジルコニア系多孔質体を得る第４工程、を有するジルコニア系多孔質体の製造方法」が記載されている。 The production method is “a method for producing a zirconia-based porous material, (1) a sulfating agent (a reagent for producing a sulfate) at 80 ° C. or higher and lower than 95 ° C. and 80 ° C. or higher and lower than 95 ° C. Prepared by mixing a basic zirconium sulfate-containing reaction solution A prepared by mixing a zirconium salt solution, a sulfating agent of 65 to 80 ° C., and a zirconium salt solution of 65 to 80 ° C. A first step of mixing with the basic zirconium sulfate-containing reaction solution B, (2) a second step of aging the reaction solution obtained in the first step at 95 ° C. or higher, and (3) mixing obtained in the second step. A third step of neutralizing the basic zirconium sulfate by adding an alkali to the solution to form zirconium hydroxide, and (4) heat-treating the zirconium hydroxide, The fourth step of obtaining a Konia based porous body, describes a method for producing a zirconia porous body "having a.
特許文献３の実施例には、１０００℃で３時間熱処理後の全気孔容量の最大値が０．７ｃｃ／ｇであると記載されている。このように、全気孔容量の耐熱性は改善されてきているが、一層の改善が求められている。
本発明は、１０００℃で３時間熱処理後の全細孔容積が少なくとも０．７５ｍｌ／ｇであり、且つ、１０００℃で３時間熱処理後の１０〜１００ｎｍの直径を有する細孔の合計容積が全細孔容積の少なくとも３０％である、全細孔容積の耐熱性が改善された多孔質ジルコニア系粉末を提供することを目的とする。また、当該粉末を簡便に得るための製造方法を提供することを目的とする。 In the present invention, the total pore volume after heat treatment at 1000 ° C. for 3 hours is at least 0.75 ml / g, and the total volume of pores having a diameter of 10 to 100 nm after heat treatment at 1000 ° C. for 3 hours is An object of the present invention is to provide a porous zirconia-based powder having an improved heat resistance of the total pore volume, which is at least 30% of the pore volume. Moreover, it aims at providing the manufacturing method for obtaining the said powder simply.
本発明者は、上記目的を達成するために鋭意研究した結果、特定の製造方法を採用する場合には、全細孔容積の耐熱性が改善された多孔質ジルコニア系粉末が簡便に得られることを見出し、本発明を完成するに至った。 As a result of intensive studies to achieve the above object, the present inventor can easily obtain a porous zirconia-based powder having improved heat resistance of the total pore volume when a specific production method is adopted. As a result, the present invention has been completed.
即ち、本発明は下記の多孔質ジルコニア系粉末及びその製造方法に関する。
１． １０００℃で３時間熱処理後の全細孔容積が少なくとも０．７５ｍｌ／ｇであり、且つ、１０００℃で３時間熱処理後の１０〜１００ｎｍの直径を有する細孔の合計容積が全細孔容積の少なくとも３０％であることを特徴とする多孔質ジルコニア系粉末。
２． １０００℃で３時間熱処理後の比表面積が少なくとも３５ｍ２／ｇである、上記項１に記載の多孔質ジルコニア系粉末。
３． １１００℃で３時間熱処理後の比表面積が少なくとも１０ｍ２／ｇである、上記項１又は２に記載の多孔質ジルコニア系粉末。
４． Ｙ、Ｓｃ、希土類金属、遷移金属元素、アルカリ土類金属、Ａｌ、Ｉｎ、Ｓｉ、Ｓｎ、Ｂｉ及びＺｎからなる群から選ばれる１種以上の金属の酸化物を１〜６０％含有する、上記項１〜３のいずれかに記載の多孔質ジルコニア系粉末。
５． ジルコニウム塩溶液に硫酸塩化剤を添加することにより塩基性硫酸ジルコニウムを生成させ、次に前記塩基性硫酸ジルコニウムを中和することにより水酸化ジルコニウムを生成させ、次に前記水酸化ジルコニウムを熱処理することにより多孔質ジルコニア系粉末を製造する方法であって、前記ジルコニウム塩溶液に前記硫酸塩化剤を添加する際に、オートクレーブ中で、温度１００℃以上の前記ジルコニウム塩溶液に前記硫酸塩化剤を添加することを特徴とする多孔質ジルコニア系粉末の製造方法。
６． 前記塩基性硫酸ジルコニウムを生成させた後であって前記塩基性硫酸ジルコニウムを中和する前に、Ｙ、Ｓｃ、希土類金属、遷移金属元素、アルカリ土類金属、Ａｌ、Ｉｎ、Ｓｉ、Ｓｎ、Ｂｉ及びＺｎからなる群から選ばれる１種以上の金属の塩を添加する、上記項５に記載の製造方法。
That is, the present invention relates to the following porous zirconia powder and a method for producing the same.
1. The total pore volume after heat treatment at 1000 ° C. for 3 hours is at least 0.75 ml / g, and the total volume of pores having a diameter of 10 to 100 nm after heat treatment at 1000 ° C. for 3 hours is the total pore volume A porous zirconia-based powder characterized by being at least 30%.
2.
3.
4). 1 to 60% of an oxide of one or more metals selected from the group consisting of Y, Sc, rare earth metals, transition metal elements, alkaline earth metals, Al, In, Si, Sn, Bi and Zn, Item 4. The porous zirconia-based powder according to any one of
5. Adding a sulfating agent to a zirconium salt solution to form basic zirconium sulfate, then neutralizing the basic zirconium sulfate to form zirconium hydroxide, and then heat treating the zirconium hydroxide; The porous zirconia-based powder is produced by adding the sulfating agent to the zirconium salt solution at a temperature of 100 ° C. or higher in an autoclave when the sulfating agent is added to the zirconium salt solution. A method for producing a porous zirconia-based powder.
6). After forming the basic zirconium sulfate and before neutralizing the basic zirconium sulfate, Y, Sc, rare earth metal, transition metal element, alkaline earth metal, Al, In, Si, Sn, Bi 6. The method according to
本発明の多孔質ジルコニア系粉末は、１０００℃で３時間熱処理後の全細孔容積が少なくとも０．７５ｍｌ／ｇであり、且つ、１０００℃で３時間熱処理後の１０〜１００ｎｍの直径を有する細孔の合計容積が全細孔容積の少なくとも３０％であり、全細孔容積の耐熱性が改善されている。かかる多孔質ジルコニア系粉末は、高温条件下で使用する自動車用の三元触媒の助触媒又は触媒担体として有用である。本発明の製造方法によれば、上記粉末を簡便に製造できる。 The porous zirconia-based powder of the present invention has a total pore volume of at least 0.75 ml / g after heat treatment at 1000 ° C. for 3 hours and a diameter of 10 to 100 nm after heat treatment at 1000 ° C. for 3 hours. The total volume of the pores is at least 30% of the total pore volume, improving the heat resistance of the total pore volume. Such porous zirconia-based powder is useful as a promoter or catalyst support for a three-way catalyst for automobiles used under high temperature conditions. According to the production method of the present invention, the powder can be produced easily.
本発明の多孔質ジルコニア系粉末及び製造方法について詳細に説明する。 The porous zirconia-based powder and production method of the present invention will be described in detail.
なお、本発明におけるジルコニアは一般的なものであり、ハフニア等の１０％以下の不純物金属化合物を含み得る。 In addition, the zirconia in this invention is common, and can contain 10% or less of impurity metal compounds, such as hafnia.
本発明において、「％」は、特に断らない限り、重量％（＝質量％）を示す。
１．多孔質ジルコニア系粉末
本発明の多孔質ジルコニア系粉末は、１０００℃で３時間熱処理後の全細孔容積が少なくとも０．７５ｍｌ／ｇ（好ましくは少なくとも０．７９ｍｌ／ｇ）であり、且つ、１０００℃で３時間熱処理後の１０〜１００ｎｍの直径を有する細孔の合計容積が全細孔容積の少なくとも３０％（好ましくは少なくとも３３％）であることを特徴とする。
In the present invention, “%” indicates wt% (= mass%) unless otherwise specified.
1. Porous zirconia powder The porous zirconia powder of the present invention has a total pore volume of at least 0.75 ml / g (preferably at least 0.79 ml / g) after heat treatment at 1000 ° C. for 3 hours, and 1000 The total volume of pores having a diameter of 10 to 100 nm after heat treatment at 3 ° C. for 3 hours is at least 30% (preferably at least 33%) of the total pore volume.
前記熱処理後の全細孔容積が０．７５ｍｌ／ｇ未満である場合や前記熱処理後の１０〜１００ｎｍの直径を有する細孔の合計容積が全細孔容積の３０％未満である場合には、貴金属粒子を担持する触媒担体として用いる際に、貴金属粒子の分散性を維持し難く、触媒活性が低下し易い。 When the total pore volume after the heat treatment is less than 0.75 ml / g or the total volume of pores having a diameter of 10 to 100 nm after the heat treatment is less than 30% of the total pore volume, When used as a catalyst carrier for supporting noble metal particles, it is difficult to maintain the dispersibility of the noble metal particles, and the catalyst activity tends to decrease.
本発明の多孔質ジルコニア系粉末は、１０００℃で３時間熱処理後の比表面積が少なくとも３５ｍ２／ｇであることが好ましい。この中でも、少なくとも４０ｍ２／ｇであることがより好ましい。 The porous zirconia-based powder of the present invention preferably has a specific surface area of at least 35 m 2 / g after heat treatment at 1000 ° C. for 3 hours. Among these, it is more preferable that it is at least 40 m 2 / g.
前記熱処理後の比表面積が３５ｍ２／ｇ未満である場合には、比表面積の減少に基づく貴金属粒子の焼結促進により、触媒活性が低下し易い。 When the specific surface area after the heat treatment is less than 35 m 2 / g, the catalytic activity tends to be lowered due to the promotion of sintering of the noble metal particles based on the decrease in the specific surface area.
なお、本発明の多孔質ジルコニア系粉末は、１１００℃で３時間熱処理後の比表面積が少なくとも１０ｍ２／ｇであることが好ましい。この中でも、少なくとも２０ｍ２／ｇであることがより好ましい。 The porous zirconia-based powder of the present invention preferably has a specific surface area of at least 10 m 2 / g after heat treatment at 1100 ° C. for 3 hours. Among these, it is more preferable that it is at least 20 m 2 / g.
本発明の多孔質ジルコニア系粉末は、Ｙ、Ｓｃ、希土類金属、遷移金属元素、アルカリ土類金属、Ａｌ、Ｉｎ、Ｓｉ、Ｓｎ、Ｂｉ及びＺｎからなる群から選ばれる１種以上の金属の酸化物を１〜６０％含有することが好ましい。この中でも、金属の酸化物を５〜５５％含有することがより好ましい。 The porous zirconia-based powder of the present invention is an oxidation of one or more metals selected from the group consisting of Y, Sc, rare earth metals, transition metal elements, alkaline earth metals, Al, In, Si, Sn, Bi, and Zn. It is preferable to contain 1 to 60% of the product. Among these, it is more preferable to contain 5-55% of metal oxides.
希土類金属としては、例えば、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ等のランタノイド元素が挙げられる。 Examples of rare earth metals include lanthanoid elements such as La, Ce, Pr, and Nd.
遷移金属元素としては、例えば、Ｔｉ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｍｏ、Ｗ等が挙げられる。 Examples of the transition metal element include Ti, Cr, Mn, Fe, Co, Ni, Cu, Mo, and W.
アルカリ土類金属としては、例えば、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ等が挙げられる。 Examples of the alkaline earth metal include Mg, Ca, Sr, Ba and the like.
これらの金属の中でも、特にＳｃ、Ｙ、希土類金属は、酸化ジルコニウム（ジルコニア）と安定な複合酸化物を形成する点で好ましい。 Among these metals, Sc, Y, and rare earth metals are particularly preferable because they form a stable composite oxide with zirconium oxide (zirconia).
上記含有量が１％未満の場合には、添加による効果が発揮され難い。他方、含有量が６０％を超える場合には、全細孔容積の耐熱性が不十分となり易い。 When the content is less than 1%, the effect of addition is hardly exhibited. On the other hand, if the content exceeds 60%, the heat resistance of the total pore volume tends to be insufficient.
図１、図２は、実施例１、比較例１で得られたジルコニア系粉末のＴＥＭ写真を示している。図１から明らかなように、本発明のジルコニア系粉末は、凝集が非常に弱い凝集粒子であることが分かる。他方、図２（比較例１）は凝集が強い。 1 and 2 show TEM photographs of the zirconia-based powders obtained in Example 1 and Comparative Example 1. FIG. As is clear from FIG. 1, it can be seen that the zirconia-based powder of the present invention is agglomerated particles having very weak agglomeration. On the other hand, FIG. 2 (Comparative Example 1) has strong aggregation.
このように、凝集が非常に弱いことにより、高温（１０００℃以上）において粒子同士の焼結が起こらず、初期状態の全細孔容積、その分布並びに比表面積を保持させることができるものと考えられる。
２．多孔質ジルコニア系粉末の製造方法
本発明の製造方法は、ジルコニウム塩溶液に硫酸塩化剤（硫酸塩を生成させる試薬であって、本発明ではジルコニウムイオンと反応して塩基性硫酸ジルコニウムを生成させる）を添加することにより塩基性硫酸ジルコニウムを生成させ、次に前記塩基性硫酸ジルコニウムを中和することにより水酸化ジルコニウムを生成させ、次に前記水酸化ジルコニウムを熱処理することにより多孔質ジルコニア系粉末を製造する方法であって、前記ジルコニウム塩溶液に前記硫酸塩化剤を添加する際に、オートクレーブ中で、温度１００℃以上の前記ジルコニウム塩溶液に前記硫酸塩化剤を添加することを特徴とする。
Thus, it is considered that the aggregation is very weak, so that the particles do not sinter at a high temperature (1000 ° C. or higher), and the total pore volume in the initial state, its distribution and specific surface area can be maintained. It is done.
2. Method for Producing Porous Zirconia Powder The production method of the present invention is a sulfating agent in a zirconium salt solution (a reagent for producing a sulfate, which reacts with zirconium ions in the present invention to produce basic zirconium sulfate). To form a basic zirconium sulfate, then neutralize the basic zirconium sulfate to produce zirconium hydroxide, and then heat-treat the zirconium hydroxide to obtain a porous zirconia-based powder. In the production method, when the sulfating agent is added to the zirconium salt solution, the sulfating agent is added to the zirconium salt solution at a temperature of 100 ° C. or higher in an autoclave.
ジルコニウム塩としては、ジルコニウムイオンを供給するものであればよく、例えば、オキシ硝酸ジルコニウム、オキシ塩化ジルコニウム、硝酸ジルコニウム等を使用できる。これらは１種又は２種以上で使用できる。この中でも、工業的規模での生産性が高い点でオキシ塩化ジルコニウムが好ましい。 Any zirconium salt may be used as long as it supplies zirconium ions. For example, zirconium oxynitrate, zirconium oxychloride, zirconium nitrate or the like can be used. These can be used alone or in combination of two or more. Among these, zirconium oxychloride is preferable in terms of high productivity on an industrial scale.
ジルコニウム塩溶液を作るための溶媒としては、ジルコニウム塩の種類に応じて選択すればよい。通常は水（純水、イオン交換水、以下同様）が好ましい。 What is necessary is just to select as a solvent for making a zirconium salt solution according to the kind of zirconium salt. Usually, water (pure water, ion-exchanged water, the same applies hereinafter) is preferable.
ジルコニウム塩溶液の濃度は特に制限されないが、一般的には溶媒１０００ｇ中に酸化ジルコニウム（ＺｒＯ２）として５〜２５０ｇ（特に２０〜１５０ｇ）含有されることが望ましい。 The concentration of the zirconium salt solution is not particularly limited, but it is generally desirable that 5-250 g (particularly 20-150 g) of zirconium oxide (ZrO 2 ) is contained in 1000 g of the solvent.
硫酸塩化剤としては、ジルコニウムイオンと反応して硫酸塩を生成させるもの（即ち、硫酸塩化させる試薬）であれば限定されず、例えば、硫酸ナトリウム、硫酸カリウム、硫酸アンモニウム等が例示される。硫酸塩化剤は、粉末状、溶液状等のいずれの形態でもよいが、溶液（特に水溶液）が好ましい。溶液を用いる場合の溶液の濃度は適宜設定できる。 The sulfating agent is not limited as long as it reacts with zirconium ions to generate a sulfate (that is, a reagent for sulfating), and examples thereof include sodium sulfate, potassium sulfate, and ammonium sulfate. The sulfating agent may be in any form such as powder or solution, but is preferably a solution (particularly an aqueous solution). When using a solution, the concentration of the solution can be set as appropriate.
硫酸塩化剤は、硫酸根（ＳＯ４ ２−）／ＺｒＯ２の重量比が０．３〜０．６となるように添加することが好ましい。また、混合液のフリーの酸濃度は、０．２〜２．２Ｎ（規定）とすることが好ましい。フリーの酸としては、硫酸、硝酸、塩酸等が例示される。フリーの酸の種類は限定されないが、塩酸が工業的規模での生産性が高い点で好ましい。 The sulfating agent is preferably added so that the weight ratio of sulfate radical (SO 4 2− ) / ZrO 2 is 0.3 to 0.6. Moreover, it is preferable that the free acid density | concentration of a liquid mixture shall be 0.2-2.2N (regulation). Examples of the free acid include sulfuric acid, nitric acid, hydrochloric acid and the like. Although the kind of free acid is not limited, hydrochloric acid is preferable in terms of high productivity on an industrial scale.
ジルコニウム塩溶液と硫酸塩化剤は、通常６５℃以上の温度において反応し、塩基性硫酸ジルコニウムが生成する。本発明においては、オートクレーブ中で、温度１００℃以上（好ましくは１１０〜１５０℃）のジルコニウム塩溶液に硫酸塩化剤を添加することによって塩基性硫酸ジルコニウムを生成させる。 The zirconium salt solution and the sulfating agent usually react at a temperature of 65 ° C. or higher to produce basic zirconium sulfate. In the present invention, basic zirconium sulfate is produced by adding a sulfating agent to a zirconium salt solution at a temperature of 100 ° C. or higher (preferably 110 to 150 ° C.) in an autoclave.
ジルコニウム塩溶液の温度が１００℃未満の場合には、硫酸塩化の反応が遅く、大きな凝集粒子が生成され易くなるために好ましくない。そのため、本発明では、温度を１００℃以上とすることを必須としている。 When the temperature of the zirconium salt solution is less than 100 ° C., the reaction of sulfation is slow, and large aggregated particles are likely to be generated, which is not preferable. Therefore, in the present invention, it is essential to set the temperature to 100 ° C. or higher.
硫酸塩化の際の圧力条件は限定されないが、１．０２×１０５〜４．９１×１０５Ｐａが好ましく、１．４５×１０５〜４．９１×１０５Ｐａがより好ましい。 The pressure conditions during the sulfuric acid chlorides is not limited, but is preferably 1.02 × 10 5 ~4.91 × 10 5 Pa, more preferably 1.45 × 10 5 ~4.91 × 10 5 Pa.
硫酸塩化後、オートクレーブ中において反応液を１０〜６０分保持し、生成した塩基性硫酸ジルコニウムを熟成させることが好ましい。塩基性硫酸ジルコニウムとしては限定されないが、例えば、ＺｒＯＳＯ４・ＺｒＯ２、５ＺｒＯ２・３ＳＯ３、７ＺｒＯ２・３ＳＯ３等の化合物の水和物が例示される。なお、塩基性硫酸ジルコニウムは、これらの１種又は２種以上の混合物でもよい。
After sulfation, it is preferable to hold the reaction solution in an autoclave for 10 to 60 minutes to age the produced basic zirconium sulfate. The basic zirconium sulfate but are not limited to, for example, hydrates of ZrOSO 4 · ZrO 2, 5ZrO 2 ·
本発明では、高温条件下で硫酸塩化剤を添加することにより、塩基性硫酸ジルコニウムの生成が急速に促進される。これにより、塩基性硫酸ジルコニウムの核成長が進まず、凝集の非常に弱い凝集粒子が生成する。この凝集粒子を中和及び焼成することにより得られる本発明のジルコニア系粉末（粒子）は、１０００℃以上の高温においても粒子同士の焼結が起こらず、初期状態の全細孔容積、その分布及び比表面積を維持し易いと考えられる。 In the present invention, the formation of basic zirconium sulfate is rapidly accelerated by adding a sulfating agent under high temperature conditions. Thereby, the nucleus growth of basic zirconium sulfate does not proceed, and aggregated particles having very weak aggregation are generated. The zirconia-based powder (particles) of the present invention obtained by neutralizing and calcining the aggregated particles does not sinter between particles even at a high temperature of 1000 ° C. or higher, and the total pore volume in the initial state and its distribution It is considered that the specific surface area can be easily maintained.
硫酸塩化後、オートクレーブから塩基性硫酸ジルコニウム含有スラリーを取り出し、８０℃以下、好ましくは６０℃以下になるように冷却する。 After sulfation, the basic zirconium sulfate-containing slurry is taken out from the autoclave and cooled to 80 ° C. or less, preferably 60 ° C. or less.
本発明の多孔質ジルコニア系粉末に前記の金属酸化物を含有させる場合には、硫酸塩化後であって中和工程の前に、所定量のＹ、Ｓｃ、希土類金属、遷移金属元素、アルカリ土類金属、Ａｌ、Ｉｎ、Ｓｉ、Ｓｎ、Ｂｉ及びＺｎからなる群から選ばれる１種又は２種以上の金属の塩を添加することが好ましい。 When the porous zirconia-based powder of the present invention contains the metal oxide, a predetermined amount of Y, Sc, rare earth metal, transition metal element, alkaline earth, after sulfation and before the neutralization step. It is preferable to add a salt of one or more metals selected from the group consisting of similar metals, Al, In, Si, Sn, Bi and Zn.
次に、塩基性硫酸ジルコニウムをアルカリで中和することにより、水酸化ジルコニウムとする。アルカリとしては限定されず、例えば、水酸化アンモニウム、重炭酸アンモニウム、水酸化ナトリウム、水酸化カリウム等が使用できる。この中でも、工業的なコスト面から水酸化ナトリウムが好ましい。 Next, the basic zirconium sulfate is neutralized with an alkali to form zirconium hydroxide. It is not limited as an alkali, For example, ammonium hydroxide, ammonium bicarbonate, sodium hydroxide, potassium hydroxide etc. can be used. Among these, sodium hydroxide is preferable from the viewpoint of industrial cost.
アルカリの添加量は、塩基性硫酸ジルコニウムの溶液から沈殿物として水酸化ジルコニウムを生成させることができれば特に限定されない。通常は上記溶液のｐＨが１１以上、好ましくは１２以上となるように添加する。 The amount of alkali added is not particularly limited as long as zirconium hydroxide can be produced as a precipitate from a basic zirconium sulfate solution. Usually, the solution is added so that the pH of the solution is 11 or more, preferably 12 or more.
中和反応後は、水酸化ジルコニウム含有溶液を３５〜６０℃で１時間以上保持することが好ましい。これにより、生成した沈殿が熟成されるとともに、濾別が容易となる。 After the neutralization reaction, it is preferable to hold the zirconium hydroxide-containing solution at 35 to 60 ° C. for 1 hour or longer. As a result, the generated precipitate is aged and is easily separated by filtration.
次に、水酸化ジルコニウムを固液分離法により回収する。例えば、濾過、遠心分離、デカンテーション等が利用できる。 Next, zirconium hydroxide is recovered by a solid-liquid separation method. For example, filtration, centrifugation, decantation, etc. can be used.
水酸化ジルコニウムを回収後、水酸化ジルコニウムを水洗し、付着している不純物を除去することが好ましい。 After collecting the zirconium hydroxide, it is preferable to wash the zirconium hydroxide with water to remove the adhering impurities.
水酸化ジルコニウムは、自然乾燥又は加熱乾燥により乾燥してもよい。必要に応じて、乾燥処理後に粉砕処理、分級処理等を実施してもよい。 Zirconium hydroxide may be dried by natural drying or heat drying. If necessary, a pulverization process, a classification process, or the like may be performed after the drying process.
最後に、水酸化ジルコニウムを熱処理することにより、多孔質ジルコニア系粉末が得られる。熱処理温度は限定的ではないが、４００〜９００℃程度で１〜５時間程度が好ましい。熱処理雰囲気は、大気中又は酸化性雰囲気中が好ましい。 Finally, a porous zirconia powder is obtained by heat-treating zirconium hydroxide. The heat treatment temperature is not limited, but is preferably about 400 to 900 ° C. and about 1 to 5 hours. The heat treatment atmosphere is preferably in the air or in an oxidizing atmosphere.
得られた多孔質ジルコニア系粉末は、粉砕してもよい。例えば、遊星ミル、ボールミル、ジェットミル等の粉砕機を利用できる。 The obtained porous zirconia-based powder may be pulverized. For example, a pulverizer such as a planetary mill, a ball mill, or a jet mill can be used.
以下に実施例及び比較例を示して本発明を具体的に説明する。但し、本発明は実施例に限定されない。 The present invention will be specifically described below with reference to examples and comparative examples. However, the present invention is not limited to the examples.
比表面積、全細孔容積の測定方法は次の通りとした。
（１）比表面積
比表面積計（「フローソーフ゛-II」マイクロメリティクス製）を用いてＢＥＴ法で測定した。
（２）全細孔容積
細孔分布測定装置（Pore Master 60-GT）を用いて水銀圧入法で測定した。測定範囲は０．００３６〜１０．３μｍとした。
The specific surface area and total pore volume were measured as follows.
(1) Specific surface area Measured by the BET method using a specific surface area meter ("Flowsorb-II" manufactured by Micromeritics).
(2) Total pore volume It measured by the mercury intrusion method using the pore distribution measuring apparatus (Pore Master 60-GT). The measurement range was 0.0036 to 10.3 μm.
表１中の「Fresh」は、水酸化ジルコニウムを６００℃×５時間熱処理して得られた酸化物を示す。また、「１０００℃、３時間後」は、上記酸化物を更に１０００℃×３時間熱処理したものを示す。これらは、熱処理の後、常温まで冷却してから比表面積及び全細孔容積を測定した。 “Fresh” in Table 1 represents an oxide obtained by heat-treating zirconium hydroxide at 600 ° C. for 5 hours. “After 3 hours at 1000 ° C.” indicates that the oxide is further heat-treated at 1000 ° C. for 3 hours. These were cooled to room temperature after heat treatment, and then the specific surface area and total pore volume were measured.
実施例１
オキシ塩化ジルコニウム・８水和物１８７ｇ（ＺｒＯ２換算：７２ｇ）をイオン交換水に溶解し、次に３５％塩酸及びイオン交換水により酸濃度が０．６７Ｎ、ＺｒＯ２濃度が４ｗ／ｖ％となるように調整した。
Example 1
187 g of zirconium oxychloride octahydrate (ZrO 2 conversion: 72 g) was dissolved in ion exchange water, and then the acid concentration was 0.67 N and the ZrO 2 concentration was 4 w / v% with 35% hydrochloric acid and ion exchange water. It adjusted so that it might become.
得られた溶液をオートクレーブに入れて圧力を２×１０５Ｐａとし、１２０℃まで昇温させて同温度で５％硫酸ナトリウム（硫酸塩化剤）１０６５ｇを添加し、更に１５分間保持した。硫酸塩化後、室温になるまで放冷し、塩基性硫酸ジルコニウム含有スラリーを得た。 The obtained solution was put into an autoclave to adjust the pressure to 2 × 10 5 Pa, the temperature was raised to 120 ° C., 1065 g of 5% sodium sulfate (sulfating agent) was added at the same temperature, and the mixture was further maintained for 15 minutes. After sulfation, the mixture was allowed to cool to room temperature to obtain a basic zirconium sulfate-containing slurry.
塩基性硫酸ジルコニウム含有スラリーに硝酸セリウム溶液２１０ｇ（ＣｅＯ２換算：２１ｇ）、硝酸ランタン溶液２０ｇ（Ｌａ２Ｏ３換算：２ｇ）及び硝酸ネオジム溶液５０ｇ（Ｎｄ２Ｏ３換算：５ｇ）を添加した。次に２５％水酸化ナトリウム（中和用アルカリ）５００ｇを６０分間かけて添加した。この中和により、水酸化ジルコニウムを生成させた。 To the basic zirconium sulfate-containing slurry, 210 g of cerium nitrate solution (CeO 2 conversion: 21 g), 20 g of lanthanum nitrate solution (La 2 O 3 conversion: 2 g) and 50 g of neodymium nitrate solution (Nd 2 O 3 conversion: 5 g) were added. Next, 500 g of 25% sodium hydroxide (alkali for neutralization) was added over 60 minutes. This neutralization produced zirconium hydroxide.
次に、水酸化ジルコニウム含有スラリーを濾過・水洗した後、６００℃で５時間焼成して酸化物を得た。酸化物は乳鉢で２０μｍ以下になるまで粉砕した。 Next, the zirconium hydroxide-containing slurry was filtered and washed with water, and then fired at 600 ° C. for 5 hours to obtain an oxide. The oxide was pulverized in a mortar until it became 20 μm or less.
上記粉砕物の組成（酸化物換算）、比表面積（ＳＡ）及び３種類の熱処理後の比表面積（Aged SA ※1〜※3）を表１に示す。また、上記粉砕物の全細孔容積（Fresh）及び２種類の熱処理後の全細孔容積も示す。更に、全細孔容積の測定結果（グラフ）を図３に示す。 Table 1 shows the composition of the pulverized product (as oxide), specific surface area (SA), and specific surface areas after three types of heat treatment (Aged SA * 1 to * 3). The total pore volume (Fresh) of the pulverized product and the total pore volume after two types of heat treatment are also shown. Furthermore, the measurement result (graph) of the total pore volume is shown in FIG.
実施例２
オキシ塩化ジルコニウム・８水和物１１７ｇ（ＺｒＯ２換算：４５ｇ）をイオン交換水に溶解し、次に３５％塩酸及びイオン交換水により酸濃度が０．６７Ｎ、ＺｒＯ２濃度が４ｗ／ｖ％となるように調整した。
Example 2
117 g of zirconium oxychloride octahydrate (ZrO 2 conversion: 45 g) was dissolved in ion-exchanged water, and then the acid concentration was 0.67 N and the ZrO 2 concentration was 4 w / v% with 35% hydrochloric acid and ion-exchanged water. It adjusted so that it might become.
得られた溶液をオートクレーブに入れて圧力を２×１０５Ｐａとし、１２０℃まで昇温させて同温度で５％硫酸ナトリウム（硫酸塩化剤）６６５ｇを添加し、更に１５分間保持した。硫酸塩化後、室温になるまで放冷し、塩基性硫酸ジルコニウム含有スラリーを得た。 The obtained solution was put into an autoclave, the pressure was adjusted to 2 × 10 5 Pa, the temperature was raised to 120 ° C., 665 g of 5% sodium sulfate (sulfating agent) was added at the same temperature, and the mixture was further maintained for 15 minutes. After sulfation, the mixture was allowed to cool to room temperature to obtain a basic zirconium sulfate-containing slurry.
塩基性硫酸ジルコニウム含有スラリーに硝酸セリウム溶液４５０ｇ（ＣｅＯ２換算：４５ｇ）、硝酸ランタン溶液３０ｇ（Ｌａ２Ｏ３換算：３ｇ）及び硝酸プラセオジム溶液７０ｇ（Ｐｒ６Ｏ１１換算：７ｇ）を添加した。次に２５％水酸化ナトリウム（中和用アルカリ）５００ｇを６０分間かけて添加した。この中和により、水酸化ジルコニウムを生成させた。 To the basic zirconium sulfate-containing slurry, 450 g of cerium nitrate solution (CeO 2 conversion: 45 g), 30 g of lanthanum nitrate solution (La 2 O 3 conversion: 3 g), and 70 g of praseodymium nitrate solution (Pr 6 O 11 conversion: 7 g) were added. Next, 500 g of 25% sodium hydroxide (alkali for neutralization) was added over 60 minutes. This neutralization produced zirconium hydroxide.
次に、水酸化ジルコニウム含有スラリーを濾過・水洗した後、６００℃で５時間焼成して酸化物を得た。酸化物は乳鉢で２０μｍ以下になるまで粉砕した。 Next, the zirconium hydroxide-containing slurry was filtered and washed with water, and then fired at 600 ° C. for 5 hours to obtain an oxide. The oxide was pulverized in a mortar until it became 20 μm or less.
上記粉砕物の組成（酸化物換算）、比表面積（ＳＡ）及び３種類の熱処理後の比表面積（Aged SA ※1〜※3）を表１に示す。また、上記粉砕物の全細孔容積（Fresh）及び２種類の熱処理後の全細孔容積も示す。 Table 1 shows the composition of the pulverized product (as oxide), specific surface area (SA), and specific surface areas after three types of heat treatment (Aged SA * 1 to * 3). The total pore volume (Fresh) of the pulverized product and the total pore volume after two types of heat treatment are also shown.
比較例１
オキシ塩化ジルコニウム・８水和物１８７ｇ（ＺｒＯ２換算：７２ｇ）をイオン交換水に溶解し、次に３５％塩酸及びイオン交換水により酸濃度が０．６７Ｎ、ＺｒＯ２濃度が４ｗ／ｖ％となるように調整した。
Comparative Example 1
187 g of zirconium oxychloride octahydrate (ZrO 2 conversion: 72 g) was dissolved in ion exchange water, and then the acid concentration was 0.67 N and the ZrO 2 concentration was 4 w / v% with 35% hydrochloric acid and ion exchange water. It adjusted so that it might become.
得られた溶液を６０℃まで昇温させて同温度で５％硫酸ナトリウム（硫酸塩化剤）１０６５ｇを添加した。次に９５℃まで昇温させて同温度で１５分保持後、室温になるまで放冷し、塩基性硫酸ジルコニウム含有スラリーを得た。 The resulting solution was heated to 60 ° C., and 1065 g of 5% sodium sulfate (sulfating agent) was added at the same temperature. Next, the temperature was raised to 95 ° C., held at the same temperature for 15 minutes, and then allowed to cool to room temperature to obtain a basic zirconium sulfate-containing slurry.
塩基性硫酸ジルコニウム含有スラリーに硝酸セリウム溶液２１０ｇ（ＣｅＯ２換算：２１ｇ）、硝酸ランタン溶液２０ｇ（Ｌａ２Ｏ３換算：２ｇ）及び硝酸ネオジム溶液５０ｇ（Ｎｄ２Ｏ３換算：５ｇ）を添加した。次に２５％水酸化ナトリウム（中和用アルカリ）５００ｇを６０分間かけて添加した。この中和により、水酸化ジルコニウムを生成させた。 To the basic zirconium sulfate-containing slurry, 210 g of cerium nitrate solution (CeO 2 conversion: 21 g), 20 g of lanthanum nitrate solution (La 2 O 3 conversion: 2 g) and 50 g of neodymium nitrate solution (Nd 2 O 3 conversion: 5 g) were added. Next, 500 g of 25% sodium hydroxide (alkali for neutralization) was added over 60 minutes. This neutralization produced zirconium hydroxide.
次に、水酸化ジルコニウム含有スラリーを濾過・水洗した後、６００℃で５時間焼成して酸化物を得た。酸化物は乳鉢で２０μｍ以下になるまで粉砕した。 Next, the zirconium hydroxide-containing slurry was filtered and washed with water, and then fired at 600 ° C. for 5 hours to obtain an oxide. The oxide was pulverized in a mortar until it became 20 μm or less.
上記粉砕物の組成（酸化物換算）、比表面積（ＳＡ）及び３種類の熱処理後の比表面積（Aged SA ※1〜※3）を表１に示す。また、上記粉砕物の全細孔容積（Fresh）及び２種類の熱処理後の全細孔容積も示す。更に、全細孔容積の測定結果（グラフ）を図４に示す。 Table 1 shows the composition of the pulverized product (as oxide), specific surface area (SA), and specific surface areas after three types of heat treatment (Aged SA * 1 to * 3). The total pore volume (Fresh) of the pulverized product and the total pore volume after two types of heat treatment are also shown. Furthermore, the measurement result (graph) of the total pore volume is shown in FIG.
※１ …１０００℃×３時間熱処理後
※２ …１１００℃×３時間熱処理後
※３ …１１５０℃×６時間熱処理後
表１から明らかなように、本発明の多孔質ジルコニア系粉末は、１０００℃で３時間熱処理後の全細孔容積が０．７５ｍｌ／ｇ以上であり、且つ１０００℃で３時間熱処理後の１０〜１００ｎｍの直径を有する細孔の合計容積が全細孔容積の３０％以上である。つまり、比較例１と比べて、実施例１、２の多孔質ジルコニア系粉末は、全細孔容積の耐熱性が向上している。また、比表面積の耐熱性の観点でも、１１００℃で３時間熱処理後における比表面積が２５ｍ２／ｇであり、比較例１と比べて耐熱性が大幅に向上していることが分かる。
* 1 After heat treatment at 1000 ° C. for 3 hours * 2 After heat treatment at 1100 ° C. for 3 hours * 3 After heat treatment at 1150 ° C. for 6 hours As shown in Table 1, the porous zirconia powder of the present invention is 1000 ° C. And the total pore volume after heat treatment for 3 hours is 0.75 ml / g or more, and the total volume of pores having a diameter of 10 to 100 nm after heat treatment at 1000 ° C. for 3 hours is 30% or more of the total pore volume It is. That is, as compared with Comparative Example 1, the porous zirconia-based powders of Examples 1 and 2 have improved heat resistance of the total pore volume. Also, from the viewpoint of heat resistance of the specific surface area, the specific surface area after heat treatment at 1100 ° C. for 3 hours is 25 m 2 / g, which indicates that the heat resistance is significantly improved as compared with Comparative Example 1.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10182155A (en) * | 1996-10-07 | 1998-07-07 | Toyota Central Res & Dev Lab Inc | Multiple oxide, multiple oxide support and catalyst containing the multiple oxide |
| JP2000319019A (en) * | 1999-03-05 | 2000-11-21 | Daiichi Kigensokagaku Kogyo Co Ltd | Zirconium-cerium based compound oxide and manufacture of the same |
| JP2006036576A (en) * | 2004-07-26 | 2006-02-09 | Daiichi Kigensokagaku Kogyo Co Ltd | Zirconia-based porous body and its production method |
| JP2007197311A (en) * | 2005-12-28 | 2007-08-09 | Daiichi Kigensokagaku Kogyo Co Ltd | Cerium-zirconium composite oxide and method for producing the same |
-
2007
- 2007-08-14 JP JP2007211368A patent/JP5063252B2/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10182155A (en) * | 1996-10-07 | 1998-07-07 | Toyota Central Res & Dev Lab Inc | Multiple oxide, multiple oxide support and catalyst containing the multiple oxide |
| JP2000319019A (en) * | 1999-03-05 | 2000-11-21 | Daiichi Kigensokagaku Kogyo Co Ltd | Zirconium-cerium based compound oxide and manufacture of the same |
| JP2006036576A (en) * | 2004-07-26 | 2006-02-09 | Daiichi Kigensokagaku Kogyo Co Ltd | Zirconia-based porous body and its production method |
| JP2007197311A (en) * | 2005-12-28 | 2007-08-09 | Daiichi Kigensokagaku Kogyo Co Ltd | Cerium-zirconium composite oxide and method for producing the same |
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| JP2012533499A (en) * | 2009-07-17 | 2012-12-27 | ロデイア・オペラシヨン | Composition comprising cerium oxide and zirconium oxide with specific porosity, its preparation method and its use in catalysis |
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