JP2000247641A - Zirconium hydroxide and its production - Google Patents
Zirconium hydroxide and its productionInfo
- Publication number
- JP2000247641A JP2000247641A JP11057256A JP5725699A JP2000247641A JP 2000247641 A JP2000247641 A JP 2000247641A JP 11057256 A JP11057256 A JP 11057256A JP 5725699 A JP5725699 A JP 5725699A JP 2000247641 A JP2000247641 A JP 2000247641A
- Authority
- JP
- Japan
- Prior art keywords
- hydroxide
- zirconium
- zirconium hydroxide
- solid
- solid acidic
- 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
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 44
- 230000002378 acidificating effect Effects 0.000 claims abstract description 31
- 239000007864 aqueous solution Substances 0.000 claims abstract description 17
- 239000002002 slurry Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 15
- 238000000862 absorption spectrum Methods 0.000 claims abstract description 14
- 238000010521 absorption reaction Methods 0.000 claims abstract description 10
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 9
- 150000003754 zirconium Chemical class 0.000 claims abstract description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 30
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 29
- 239000003054 catalyst Substances 0.000 claims description 20
- 239000011973 solid acid Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 15
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 15
- 229910021529 ammonia Inorganic materials 0.000 claims description 14
- 238000002441 X-ray diffraction Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000003795 desorption Methods 0.000 claims description 7
- 238000001179 sorption measurement Methods 0.000 claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 3
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 14
- 238000005259 measurement Methods 0.000 abstract description 11
- 239000000243 solution Substances 0.000 abstract description 5
- 238000001035 drying Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000003377 acid catalyst Substances 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000005917 acylation reaction Methods 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- -1 inorganic acid salts Chemical class 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 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
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 241000705939 Shortia uniflora Species 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- CHCFOMQHQIQBLZ-UHFFFAOYSA-N azane;phthalic acid Chemical compound N.N.OC(=O)C1=CC=CC=C1C(O)=O CHCFOMQHQIQBLZ-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- HQWKKEIVHQXCPI-UHFFFAOYSA-L disodium;phthalate Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C([O-])=O HQWKKEIVHQXCPI-UHFFFAOYSA-L 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000002823 nitrates Chemical class 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
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- QRTRRDMHGTZPBF-UHFFFAOYSA-L oxygen(2-);zirconium(4+);sulfate Chemical compound [O-2].[Zr+4].[O-]S([O-])(=O)=O QRTRRDMHGTZPBF-UHFFFAOYSA-L 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、新規な水酸化ジル
コニウム及びその製造方法に関する。The present invention relates to a novel zirconium hydroxide and a method for producing the same.
【0002】[0002]
【従来技術】化学工業においては、アルキル化反応、ア
シル化反応、エステル化反応、異性化反応等の酸触媒を
必要とする反応が多数知られている。従来より、この種
の反応で用いられる酸触媒としては、例えば硫酸、フッ
化水素、リン酸、塩化アルミニウム、p−トルエンスル
ホン酸等が知られている。2. Description of the Related Art In the chemical industry, many reactions requiring an acid catalyst such as an alkylation reaction, an acylation reaction, an esterification reaction and an isomerization reaction are known. Conventionally, sulfuric acid, hydrogen fluoride, phosphoric acid, aluminum chloride, p-toluenesulfonic acid and the like have been known as an acid catalyst used in this type of reaction.
【0003】ところが、これらの酸触媒は、一般に金属
を腐食させる性質を有する。このため、反応装置に高価
な耐食材料を使用したり、あるいは反応装置に耐食処理
を施さなければならない。また、反応後において反応生
成物から酸触媒を分離回収することが困難である上、た
とえ分離回収できたとしてもアルカリ洗浄等の廃酸処理
が必要となる。また、酸触媒の再利用も、技術的・コス
ト的にも非常に困難である。[0003] However, these acid catalysts generally have the property of corroding metals. For this reason, expensive corrosion-resistant materials must be used for the reactor, or corrosion-resistant treatment must be performed on the reactor. In addition, it is difficult to separate and recover the acid catalyst from the reaction product after the reaction, and even if separation and recovery can be performed, waste acid treatment such as alkali washing is required. Also, it is very difficult to reuse the acid catalyst from a technical and cost standpoint.
【0004】このような状況において、固体酸性物質を
酸触媒として用いる試みが数多くなされている。この固
体酸性物質として、例えばジルコニウムに代表される周
期律表第IV族金属水酸化物又は水和酸化物を硫酸分含
有水溶液と接触させた後、350〜800℃で焼成して
なる硫酸分含有水酸化物が100質量%硫酸よりも高い
酸性度を示すことが報告されている(特公昭59−61
81号公報、特開平9−103681号公報、特開昭6
1−263922号公報、特開昭61−153140号
公報等)。一般に、これら固体酸性物質の活性は、固体
酸性が高いほど高くなることが知られている。[0004] Under such circumstances, many attempts have been made to use a solid acidic substance as an acid catalyst. As the solid acidic substance, for example, a hydroxide or hydrated oxide of Group IV metal represented by zirconium is brought into contact with an aqueous solution containing a sulfuric acid, and then calcined at 350 to 800 ° C. It has been reported that hydroxides exhibit higher acidity than 100% by mass sulfuric acid (Japanese Patent Publication No. 59-61).
No. 81, Japanese Patent Application Laid-Open No. 9-103681, Japanese Patent Application Laid-Open
1-263922, JP-A-61-153140, etc.). In general, it is known that the activity of these solid acidic substances increases as the solid acidity increases.
【0005】[0005]
【発明が解決しようとする課題】しかしながら、これら
の固体酸性物質においても、その固体酸性は十分なもの
とは言えず、なお改善すべき余地を残している。また、
安定性についてもさらなる改良が必要である。However, even in these solid acidic substances, the solid acidity cannot be said to be sufficient, and there is still room for improvement. Also,
Further improvements in stability are needed.
【0006】固体酸性の発現機構又は原理について、工
業的規模での開発と並行して多くの研究報告がなされて
いるものの、そのほとんどが2種以上の金属どうしの複
合化あるいは金属元素と非金属元素との複合化による効
果を中心に検討されているものであり(荒田一志、Petr
ochem,19,9,733(1996))、水酸化ジルコニウム又は含水
酸化ジルコニウム自体の構造的特徴あるいは化学的特性
についてはほとんど検討されていないのが現状である。
このため、これら水酸化物又は含水酸化物(水和酸化
物)を固体酸性物質として用いる場合に必要とされる特
性さえも化学的に解明されていない。Although many research reports have been made on the mechanism or principle of solid acid development in parallel with the development on an industrial scale, most of them have been reported as a composite of two or more metals or a metal element and a non-metal. It is being studied focusing on the effects of compounding with elements (Kazushi Arata, Petr
ochem, 19, 9, 733 (1996)), at present, little has been studied on the structural or chemical properties of zirconium hydroxide or hydrous zirconium hydroxide itself.
Therefore, even the properties required when these hydroxides or hydrated oxides (hydrated oxides) are used as solid acidic substances have not been elucidated chemically.
【0007】従って、本発明は、優れた固体酸性を有す
る固体酸性物質を再現性良く提供できる水酸化ジルコニ
ウムを製造すること及び上記固体酸性物質を提供するこ
とを主な目的とする。Accordingly, an object of the present invention is to produce zirconium hydroxide which can provide a solid acidic substance having excellent solid acidity with good reproducibility, and to provide the solid acidic substance.
【0008】[0008]
【課題を解決するための手段】本発明者は、鋭意研究を
重ねた結果、特定の工程を経て調製された水酸化ジルコ
ニウムがその特異な構造を有することを見出し、ついに
本発明を完成するに至った。Means for Solving the Problems As a result of intensive studies, the present inventors have found that zirconium hydroxide prepared through a specific step has a peculiar structure, and finally completed the present invention. Reached.
【0009】すなわち、本発明は、下記の水酸化ジルコ
ニウム及びその製造方法に係るものである。That is, the present invention relates to the following zirconium hydroxide and a method for producing the same.
【0010】1.赤外吸収スペクトル測定において13
00〜1700cm-1に2以上の赤外吸収帯を有する水
酸化ジルコニウム。[0010] 1. 13 in the infrared absorption spectrum measurement
Zirconium hydroxide having two or more infrared absorption bands at 00 to 1700 cm -1 .
【0011】2.可溶性ジルコニウム塩水溶液を加水分
解してスラリーを調製する第一工程、上記スラリーに塩
基を加えて水酸化物を生成させる第二工程、及び上記水
酸化物を分離回収する第三工程を有する水酸化ジルコニ
ウムの製造方法。2. Hydroxidation having a first step of preparing a slurry by hydrolyzing an aqueous solution of a soluble zirconium salt, a second step of adding a base to the slurry to form a hydroxide, and a third step of separating and recovering the hydroxide A method for producing zirconium.
【0012】[0012]
【発明の実施の形態】以下、本発明をその実施の形態に
基づき詳細に説明する。なお、本発明の水酸化ジルコニ
ウムとしては、含水酸化ジルコニウムも包含される。す
なわち、水酸化ジルコニウムは一般式ZrO(OH)2
・nH2O(n>0)で示される化合物であり、含水酸
化ジルコニウムは一般式ZrO2・nH2O(n>0)で
示される化合物であり、本発明は双方を含む。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail based on its embodiments. The zirconium hydroxide of the present invention also includes hydrous zirconium hydroxide. That is, zirconium hydroxide has the general formula ZrO (OH) 2
· NH is a compound represented by the 2 O (n> 0), hydrous zirconium oxide is a compound represented by the general formula ZrO 2 · nH 2 O (n > 0), the present invention includes both.
【0013】本発明の水酸化ジルコニウムは、赤外吸収
スペクトル測定において1300〜1700cm-1に2
以上(好ましくは3以上)の赤外吸収帯を有する。The zirconium hydroxide of the present invention has an infrared absorption spectrum measurement of 2300 to 1700 cm -1 .
It has the above (preferably 3 or more) infrared absorption bands.
【0014】また、本発明の水酸化ジルコニウムは、3
00〜400℃での熱処理後において、酸化ジルコニウ
ムの単斜晶系に属するX線回折像を示すことが好まし
い。すなわち、本発明の水酸化ジルコニウムを加熱して
得られる酸化ジルコニウムが単斜晶系を含むものである
ことが好ましい。Further, the zirconium hydroxide of the present invention comprises 3
It is preferable to show an X-ray diffraction image belonging to a monoclinic system of zirconium oxide after heat treatment at 00 to 400 ° C. That is, the zirconium oxide obtained by heating the zirconium hydroxide of the present invention preferably contains a monoclinic system.
【0015】上記の熱処理温度については、上記範囲内
のいずれかの温度で熱処理した場合において、酸化ジル
コニウムの単斜晶系に属するX線回折像を示すものであ
れば良い。また、本発明では、酸化ジルコニウムの単斜
晶系に属するX線回折像を示す限り、他のX線回折像
(他の結晶相のピーク)が同時に発現していても良い。
言い換えれば、上記単斜晶系とともに他の結晶相が含ま
れていても良い。The above heat treatment temperature may be any as long as it shows an X-ray diffraction image belonging to the monoclinic zirconium oxide when the heat treatment is performed at any temperature within the above range. In the present invention, other X-ray diffraction images (peaks of other crystal phases) may be simultaneously expressed as long as an X-ray diffraction image belonging to a monoclinic system of zirconium oxide is shown.
In other words, other crystal phases may be contained together with the monoclinic system.
【0016】本発明の水酸化ジルコニウムの比表面積
は、特に限定されず、最終製品の用途、使用目的当に応
じて適宜設定できる。例えば、固体酸触媒、固体酸性触
媒担体等の固体酸触媒用として用いる場合は、BET比
表面積が200m2/g以上、特に250m2/g以上で
あることが好ましい。かかる比表面積を採用することに
よって、触媒材料としてより優れた効果を発揮すること
ができる。従って、後記に示すように、固体酸性組成物
用(特に触媒用、好ましくは固体酸触媒用)水酸化ジル
コニウムとして好適に用いることができる。The specific surface area of the zirconium hydroxide of the present invention is not particularly limited, and can be appropriately set according to the use and purpose of the final product. For example, when used for a solid acid catalyst such as a solid acid catalyst or a solid acidic catalyst carrier, the BET specific surface area is preferably 200 m 2 / g or more, particularly preferably 250 m 2 / g or more. By employing such a specific surface area, a more excellent effect as a catalyst material can be exhibited. Therefore, as shown below, it can be suitably used as zirconium hydroxide for solid acidic compositions (particularly for catalysts, preferably for solid acid catalysts).
【0017】本発明の水酸化ジルコニウムは、例えば可
溶性ジルコニウム塩水溶液を加水分解してスラリーを調
製する第一工程、上記スラリーに塩基を加えて水酸化物
を生成させる第二工程、及び上記水酸化物を分離回収す
る第三工程を有する製造方法により得ることができる。The zirconium hydroxide of the present invention comprises, for example, a first step of preparing a slurry by hydrolyzing an aqueous solution of a soluble zirconium salt, a second step of adding a base to the slurry to form a hydroxide, and It can be obtained by a production method having a third step of separating and recovering substances.
【0018】第一工程で使用する可溶性ジルコニウム塩
としては、水に可溶性のものであれば特に限定されず、
公知の製法で得られるもの又は市販品を用いることもで
きる。例えば、オキシ硝酸ジルコニウム等の硝酸塩、塩
化ジルコニウム、オキシ塩化ジルコニウム等の塩化物、
酢酸ジルコニウム等の酢酸塩等を用いることができる。
本発明では、この中でも、特にオキシ塩化ジルコニウム
が好ましい。The soluble zirconium salt used in the first step is not particularly limited as long as it is soluble in water.
A product obtained by a known production method or a commercially available product can also be used. For example, nitrates such as zirconium oxynitrate, zirconium chloride, chlorides such as zirconium oxychloride,
An acetate such as zirconium acetate can be used.
In the present invention, among these, zirconium oxychloride is particularly preferred.
【0019】可溶性ジルコニウム塩水溶液の濃度は、用
いる可溶性ジルコニウム塩の種類(溶解度)等に応じて
適宜設定すれば良いが、水溶液1リットル中に酸化ジル
コニウムとして10〜200g程度、好ましくは50〜
100gとすれば良い。The concentration of the aqueous solution of the soluble zirconium salt may be appropriately set according to the kind (solubility) of the soluble zirconium salt to be used.
What is necessary is just 100 g.
【0020】第一工程における加水分解の方法として
は、加水分解物を含むスラリーが生成される限りは特に
制限されない。例えば、上記水溶液に加水分解剤を添加
することにより実施することができる。加水分解剤とし
ては、例えば硫酸等の無機酸、フタル酸等の有機酸、硫
酸アンモニウム、硫酸アルミニウム等の無機酸塩、フタ
ル酸アンモニウム、フタル酸ナトリウム等の有機酸塩を
使用することができる。加水分解剤の添加量は、用いる
加水分解剤の種類、上記水溶液の種類等によって適宜変
更できるが、一般的には上記水溶液中の可溶性ジルコニ
ウム塩すべてと反応してスラリーを生成するのに十分な
量であれば良く、その化学量論量よりも過剰量の加水分
解剤を添加しても良い。The method of hydrolysis in the first step is not particularly limited as long as a slurry containing the hydrolyzate is produced. For example, it can be carried out by adding a hydrolyzing agent to the aqueous solution. Examples of the hydrolyzing agent include inorganic acids such as sulfuric acid, organic acids such as phthalic acid, inorganic acid salts such as ammonium sulfate and aluminum sulfate, and organic acid salts such as ammonium phthalate and sodium phthalate. The amount of the hydrolyzing agent added can be appropriately changed depending on the type of the hydrolyzing agent used, the type of the aqueous solution, and the like, but is generally sufficient to react with all the soluble zirconium salts in the aqueous solution to form a slurry. Any amount may be used, and a hydrolyzing agent in excess of the stoichiometric amount may be added.
【0021】次に、第二工程では、スラリーに塩基を加
えて水酸化物を生成させる。用いる塩基の種類は、特に
制限されず、例えば水酸化ナトリウム、水酸化カリウ
ム、アンモニア、炭酸ナトリウム、炭酸アンモニウム等
が使用できる。塩基の添加量は、水酸化物を生成させる
ことができれば特に限定されないが、通常はスラリーp
Hが9以上、好ましくは12.5以上となるように調整
すれば良い。Next, in the second step, a hydroxide is formed by adding a base to the slurry. The type of base used is not particularly limited, and for example, sodium hydroxide, potassium hydroxide, ammonia, sodium carbonate, ammonium carbonate, and the like can be used. The amount of the base to be added is not particularly limited as long as the hydroxide can be generated.
It may be adjusted so that H is 9 or more, preferably 12.5 or more.
【0022】最後に、第三工程として、第二工程で生成
した水酸化物を分離回収する。分離回収する方法は、公
知の固液分離方法に従えば良い。例えば、ろ過、遠心分
離法、デカンテーション等を用いることができる。これ
により、本発明水酸化ジルコニウムがいわゆる含水酸化
ジルコニウム(水酸化ジルコニウム前駆体)として得る
ことができる。分離回収後、得られた水酸化ジルコニウ
ムを必要に応じて水洗することもできる。Finally, as a third step, the hydroxide generated in the second step is separated and recovered. The method of separation and recovery may be in accordance with a known solid-liquid separation method. For example, filtration, centrifugation, decantation and the like can be used. As a result, the zirconium hydroxide of the present invention can be obtained as a so-called hydrous zirconium hydroxide (a zirconium hydroxide precursor). After separation and recovery, the obtained zirconium hydroxide can be washed with water as needed.
【0023】得られた水酸化ジルコニウムは、必要に応
じて乾燥処理すれば良い。乾燥方法は、公知の乾燥方法
によって実施すれば良く、また自然乾燥又は加熱乾燥の
いずれであっても良い。特に、本発明の水酸化ジルコニ
ウムを固体酸触用として用いる場合は、通常50℃以
上、好ましくは100〜130℃で加熱乾燥することが
好ましい。また、加熱乾燥する場合の雰囲気は、特に制
限されないが、本発明では真空中で行うことが好まし
い。真空中で加熱乾燥することにより、化学的には大気
中での二酸化炭素の吸着の防止、生産的には乾燥時間の
短縮等の効果が得られる。乾燥した後は、必要に応じて
水酸化ジルコニウムを公知の方法により粉砕しても良
い。The obtained zirconium hydroxide may be dried if necessary. The drying may be performed by a known drying method, and may be either natural drying or heat drying. In particular, when the zirconium hydroxide of the present invention is used as a solid acid catalyst, it is preferable to heat and dry at 50 ° C or higher, preferably 100 to 130 ° C. The atmosphere in the case of heating and drying is not particularly limited, but in the present invention, it is preferable to perform the drying in a vacuum. By heating and drying in a vacuum, effects such as chemically preventing carbon dioxide from adsorbing in the atmosphere and shortening the drying time in terms of productivity can be obtained. After drying, zirconium hydroxide may be pulverized by a known method, if necessary.
【0024】上記水酸化ジルコニウムから固体酸性組成
物を製造する場合には、例えば上記水酸化ジルコニウム
を硫酸、タングステン酸及びモリブデン酸の少なくとも
1種を含む水溶液で処理した後、300℃以上で焼成す
れば良い。In the case of producing a solid acidic composition from the zirconium hydroxide, for example, the zirconium hydroxide is treated with an aqueous solution containing at least one of sulfuric acid, tungstic acid and molybdic acid, and then calcined at 300 ° C. or more. Good.
【0025】硫酸、タングステン酸及びモリブデン酸
は、それ自体公知のもの又は市販品を用いれば良い。ま
た、上記水溶液の濃度は、最終製品の用途、所望の性能
等によって適宜設定することができるが、通常0.1〜
2モル/リットル程度、好ましくは0.5〜1モル/リ
ットルとすれば良い。As the sulfuric acid, tungstic acid and molybdic acid, those known per se or commercially available products may be used. The concentration of the aqueous solution can be appropriately set depending on the use of the final product, desired performance, and the like.
It may be about 2 mol / l, preferably 0.5 to 1 mol / l.
【0026】上記水溶液で処理する方法としては、例え
ば上記水溶液中に水酸化ジルコニウムを分散(又は浸
漬)させれば良い。上記水溶液に分散させる水酸化ジル
コニウムの量は、上記水溶液の濃度、担持させる硫酸量
等に応じて適宜決定することができるが、通常10〜5
00g/リットル程度、好ましくは100〜300g/
リットルとすれば良い。As a method of treating with the aqueous solution, for example, zirconium hydroxide may be dispersed (or immersed) in the aqueous solution. The amount of zirconium hydroxide dispersed in the aqueous solution can be appropriately determined according to the concentration of the aqueous solution, the amount of sulfuric acid to be supported, and the like.
About 100 g / liter, preferably 100-300 g /
It should be liter.
【0027】上記処理した後、必要に応じて公知の方法
により固液分離又は乾燥し、その後に焼成を行う。焼成
温度は、通常300℃以上、好ましくは500〜800
℃とすれば良い。焼成雰囲気は、特に制限されず、通常
は大気中とすれば良い。焼成時間は、焼成温度等に応じ
て適宜設定することができる。これにより、硫酸含有ジ
ルコニア(硫酸担持ジルコニア)等の固体酸性組成物が
得られる。After the above treatment, solid-liquid separation or drying is performed by a known method, if necessary, followed by baking. The firing temperature is usually 300 ° C. or higher, preferably 500 to 800.
° C. The firing atmosphere is not particularly limited, and may be usually in the air. The firing time can be appropriately set according to the firing temperature and the like. Thereby, a solid acidic composition such as sulfuric acid-containing zirconia (sulfuric acid-supporting zirconia) is obtained.
【0028】本発明の固体酸性組成物は、優れた固体酸
性を示す。特に、アンモニア脱離開始温度が125℃以
上であって、かつ、アンモニア吸着量が4mmol−N
H3/g以上という特性を示す。すなわち、本発明の固
体酸性組成物は、固体酸性度が強く、かつ、固体酸量が
多い。The solid acidic composition of the present invention exhibits excellent solid acidity. In particular, the ammonia desorption start temperature is 125 ° C. or higher, and the ammonia adsorption amount is 4 mmol-N
It shows a characteristic of H 3 / g or more. That is, the solid acidic composition of the present invention has a high solid acidity and a large amount of solid acid.
【0029】本発明の固体酸性組成物は、公知の固体酸
性物質と同様の用途に使用でき、特に固体酸触媒又は固
体酸性担体として好適に使用することもできる。本発明
組成物を固体酸触媒又は固体酸性触媒担体として用いる
場合は、公知の固体酸触媒又は固体酸性触媒担体と同様
の方法に従って使用することができる。The solid acidic composition of the present invention can be used for the same applications as known solid acidic substances, and in particular, can be suitably used as a solid acid catalyst or a solid acidic carrier. When the composition of the present invention is used as a solid acid catalyst or a solid acidic catalyst carrier, it can be used according to a method similar to a known solid acid catalyst or a solid acidic catalyst carrier.
【0030】[0030]
【作用】金属−酸素間の結合に起因する赤外吸収は、一
般に1000〜2000cm-1付近に現われ、中心金属
とそれに結合する酸素がすべて等価な関係にあれば赤外
吸収帯は一つしか観察されない。従来における水酸化ジ
ルコニウムも、これを加熱した場合、準安定正方晶と呼
ばれる結晶系をとる。そして、この準安定正方晶では、
金属−酸素間結合は2種であり、かつ、非常に似通った
赤外吸収帯(すなわち、実質的に1つの赤外吸収帯)が
観察される。The infrared absorption due to the metal-oxygen bond generally appears around 1000 to 2000 cm -1 . If the central metal and the oxygen bonded to it all have an equivalent relationship, there is only one infrared absorption band. Not observed. Conventional zirconium hydroxide also takes a crystal system called a metastable tetragon when heated. And in this metastable tetragon,
There are two types of metal-oxygen bonds, and very similar infrared absorption bands (ie, substantially one infrared absorption band) are observed.
【0031】これに対し、本発明の水酸化ジルコニウム
では、同様に赤外吸収スペクトルを測定した際、130
0〜1700cm-1において2つ以上の赤外吸収帯を示
す。例えば、後記に示す実施例1で調製された試料1〜
2は、1300〜1700cm-1において3つの赤外吸
収帯を示し、これは等価でない3種以上の金属−酸素間
結合を有することを示す。すなわち、本発明の水酸化ジ
ルコニウムは、一般には酸素の配位数7である単斜晶系
に属する結晶系を含み、この結晶系は酸素欠陥を有す
る。かかる酸素欠陥は、主として固体酸性が発現する場
となるので、本発明の水酸化ジルコニウムは高い固体酸
性を呈することとなる。その結果として、本発明の水酸
化ジルコニウムは固体酸触媒又は固体酸性触媒担体とし
て優れた効果を発揮することができる。On the other hand, when the zirconium hydroxide of the present invention was similarly measured for its infrared absorption spectrum,
Two or more infrared absorption bands are shown at 0 to 1700 cm -1 . For example, samples 1 to 1 prepared in Example 1 shown below
2 shows three infrared absorption bands at 1300 to 1700 cm −1 , which indicates that the compound has three or more unequal metal-oxygen bonds. That is, the zirconium hydroxide of the present invention generally includes a crystal system belonging to a monoclinic system having an oxygen coordination number of 7, and this crystal system has oxygen defects. Since such oxygen deficiency is mainly a place where solid acidity appears, the zirconium hydroxide of the present invention exhibits high solid acidity. As a result, the zirconium hydroxide of the present invention can exhibit an excellent effect as a solid acid catalyst or a solid acidic catalyst carrier.
【0032】本発明において、特に、300〜400℃
での熱処理後において酸化ジルコニウムの単斜晶系に属
するX線回折像を示す水酸化ジルコニウムは、熱処理後
も単斜晶系を維持できることから、再現性良く安定した
触媒酸性(固体酸性)を得ることができる。In the present invention, particularly, 300 to 400 ° C.
Zirconium hydroxide, which shows an X-ray diffraction image belonging to the monoclinic system of zirconium oxide after the heat treatment, can maintain the monoclinic system even after the heat treatment, so that a stable catalytic acidity (solid acidity) with good reproducibility is obtained. be able to.
【0033】[0033]
【発明の効果】本発明の製造方法によれば、従来の水酸
化ジルコニウムとは異なった結晶系を有する水酸化ジル
コニウムを得ることができる。そして、この水酸化ジル
コニウムによれば、優れた固体酸性を有する固体酸性物
質を再現性良く提供することができる。According to the production method of the present invention, zirconium hydroxide having a crystal system different from that of the conventional zirconium hydroxide can be obtained. According to the zirconium hydroxide, a solid acidic substance having excellent solid acidity can be provided with good reproducibility.
【0034】上記水酸化ジルコニウムから得られる固体
酸性組成物は、その固体酸強度が高く、しかも固体酸量
が多いことから、固体酸触媒又は固体酸性触媒担体とし
て特に有用である。従って、例えばアルキル化反応、ア
シル化反応、エステル化反応、異性化反応、その他一般
に酸触媒を必要とする反応において好適に用いることが
できる。The solid acidic composition obtained from the above zirconium hydroxide is particularly useful as a solid acid catalyst or a solid acidic catalyst carrier because of its high solid acid strength and large amount of solid acid. Therefore, it can be suitably used in, for example, an alkylation reaction, an acylation reaction, an esterification reaction, an isomerization reaction, and other reactions that generally require an acid catalyst.
【0035】[0035]
【実施例】以下に実施例を示し、本発明の特徴をより明
確にする。The following examples are provided to further clarify the features of the present invention.
【0036】実施例1 (1)水酸化ジルコニウム(試料1〜2及び比較試料
1)の調製 10重量%オキシ塩化ジルコニウム溶液1000gを1
7重量%フタル酸1000gで加水分解し、ジカルボン
酸ジルコニウムのスラリーを得た。次いで、このスラリ
ーに水酸化ナトリウム溶液をpH13となるまで添加
し、水酸化物の沈殿を生成させた。沈殿物をろ過し、水
洗した後、固形分を回収し、水酸化ジルコニウム前駆体
を得た。この前駆体を真空乾燥機中120℃で24時間
乾燥して水酸化ジルコニウム(試料1)を得た。Example 1 (1) Preparation of Zirconium Hydroxide (Samples 1 and 2 and Comparative Sample 1)
Hydrolysis was performed with 1000 g of 7% by weight phthalic acid to obtain a slurry of zirconium dicarboxylate. Next, a sodium hydroxide solution was added to the slurry until the pH reached 13, and a hydroxide precipitate was formed. After the precipitate was filtered and washed with water, the solid content was recovered to obtain a zirconium hydroxide precursor. The precursor was dried in a vacuum dryer at 120 ° C. for 24 hours to obtain zirconium hydroxide (sample 1).
【0037】10重量%オキシ塩化ジルコニウム溶液1
000gを硫酸ナトリウム60gで加水分解し、塩基性
硫酸ジルコニウムのスラリーを得た。次いで、このスラ
リーに水酸化ナトリウム溶液をpH13となるまで添加
し、水酸化物の沈殿を生成させた。沈殿物をろ過し、水
洗した後、固形分を回収し、水酸化ジルコニウム前駆体
を得た。この前駆体を真空乾燥機中120℃で24時間
乾燥して水酸化ジルコニウム(試料2)を得た。10% by weight zirconium oxychloride solution 1
000 g was hydrolyzed with 60 g of sodium sulfate to obtain a slurry of basic zirconium sulfate. Next, a sodium hydroxide solution was added to the slurry until the pH reached 13, and a hydroxide precipitate was formed. After the precipitate was filtered and washed with water, the solid content was recovered to obtain a zirconium hydroxide precursor. The precursor was dried at 120 ° C. for 24 hours in a vacuum dryer to obtain zirconium hydroxide (Sample 2).
【0038】10重量%オキシ塩化ジルコニウム水溶液
1000gにアンモニア水をpHが10.1となるまで
添加し、水酸化物の沈殿を生成させた。次いで、沈殿物
をろ過し、水洗し、水酸化ジルコニウム前駆体を得た。
この前駆体を乾燥機中120℃で24時間乾燥すること
により水酸化ジルコニウム(比較試料1)を得た。
(2)硫酸含有酸化ジルコニウム(固体酸性組成物)の
調製試料1の水酸化ジルコニウムを10重量%硫酸アン
モニウム溶液中で分散し、ろ別した後、大気中600℃
で焼成し、対応する硫酸含有酸化ジルコニウム(試料
3)を得た。同様の方法で処理することによって、試料
2から硫酸含有酸化ジルコニウム(試料4)、比較試料
1から硫酸含有酸化ジルコニウム(比較試料2)をそれ
ぞれ得た。Aqueous ammonia was added to 1000 g of a 10% by weight aqueous solution of zirconium oxychloride until the pH reached 10.1 to precipitate hydroxide. Next, the precipitate was filtered and washed with water to obtain a zirconium hydroxide precursor.
This precursor was dried in a dryer at 120 ° C. for 24 hours to obtain zirconium hydroxide (Comparative Sample 1).
(2) Preparation of Sulfuric Acid-Containing Zirconium Oxide (Solid Acidic Composition) The zirconium hydroxide of Sample 1 was dispersed in a 10% by weight ammonium sulfate solution, filtered, and then 600 ° C. in the atmosphere.
And the corresponding sulfuric acid-containing zirconium oxide (sample 3) was obtained. By treating in the same manner, zirconium oxide containing sulfuric acid from sample 2 (sample 4) and zirconium oxide containing sulfuric acid from comparative sample 1 (comparative sample 2) were obtained.
【0039】試験例1 水酸化ジルコニウムの評価 実施例1で調製された試料1〜2及び比較試料1の水酸
化ジルコニウムについて、赤外吸収スペクトル測定、X
線回折分析及び比表面積の測定をそれぞれ実施した。Test Example 1 Evaluation of zirconium hydroxide Samples 1 and 2 prepared in Example 1 and zirconium hydroxide of Comparative Sample 1 were measured for infrared absorption spectrum,
The line diffraction analysis and the measurement of the specific surface area were respectively performed.
【0040】赤外吸収スペクトル測定は、赤外吸収スペ
クトル測定装置(Herschel製;FT/IR−420)を
用いて顕微透過法にて測定した。X線回折分析は、X線
回折装置(リガク製;RAD−2C)を用いて測定し
た。比表面積は、比表面積計(MICROMERITICS製;FL
OWSORB−II)を用いて、BET法によって測定し
た。The infrared absorption spectrum was measured by a microscopic transmission method using an infrared absorption spectrum measuring apparatus (manufactured by Herschel; FT / IR-420). The X-ray diffraction analysis was measured using an X-ray diffractometer (Rigaku; RAD-2C). The specific surface area is measured using a specific surface area meter (manufactured by MICROMERITICS; FL)
OWSORB-II) was measured by the BET method.
【0041】比表面積の測定結果及び水分量を表1に示
す。赤外吸収スペクトル測定結果を図1に示す。また、
各水酸化ジルコニウムを300℃で加熱した後のX線回
折分析の結果を図2に示す。図2より、試料1及び2で
は、それぞれ28.2°及び31.5°に単斜晶系のピ
ークを有することがわかる。Table 1 shows the measurement results of the specific surface area and the water content. FIG. 1 shows the measurement results of the infrared absorption spectrum. Also,
FIG. 2 shows the results of X-ray diffraction analysis after heating each zirconium hydroxide at 300 ° C. FIG. 2 shows that Samples 1 and 2 have monoclinic peaks at 28.2 ° and 31.5 °, respectively.
【0042】[0042]
【表1】 [Table 1]
【0043】試験例2 硫酸含有酸化ジルコニウムの評価 実施例1で調製された試料3〜4及び比較試料2の硫酸
含有酸化ジルコニウムについて、赤外吸収スペクトル測
定、X線回折分析ならびにアンモニア吸着量及びアンモ
ニア脱離開始温度の測定をそれぞれ行った。Test Example 2 Evaluation of Sulfuric Acid-Containing Zirconium Oxide The samples 3 to 4 prepared in Example 1 and the sulfuric acid-containing zirconium oxide of Comparative Sample 2 were subjected to infrared absorption spectrum measurement, X-ray diffraction analysis, ammonia adsorption amount and ammonia The desorption starting temperature was measured.
【0044】赤外吸収スペクトル測定及びX線回析分析
の結果は、前記水酸化ジルコニウムの場合と同様に測定
した。また、アンモニア吸着量は、TPD測定装置(日
本ベル製;マルチタスクTPD(TPD−1−AT))
を用いて昇温脱離法にて測定した。The results of infrared absorption spectrum measurement and X-ray diffraction analysis were measured in the same manner as in the case of zirconium hydroxide. In addition, the ammonia adsorption amount was measured using a TPD measuring device (manufactured by Nippon Bell; multitask TPD (TPD-1-AT)).
Was measured by a temperature programmed desorption method.
【0045】赤外吸収スペクトルの測定結果を図3に示
す。X線回折分析の結果を図4に示す。図4では、いず
れの試料も30.2°にピークがあり、硫酸根(S
O4)により準安定正方晶系が生成していることがわか
る。また、これらの試料のアンモニア吸着量及びアンモ
ニア脱離開始温度を表2に示す。FIG. 3 shows the measurement results of the infrared absorption spectrum. The result of the X-ray diffraction analysis is shown in FIG. In FIG. 4, each sample has a peak at 30.2 °, and the sulfate group (S
It can be seen that O 4 ) forms a metastable tetragonal system. Table 2 shows the ammonia adsorption amount and the ammonia desorption start temperature of these samples.
【0046】[0046]
【表2】 [Table 2]
【0047】表2の結果より、試料3及び試料4は、比
較試料2と比べてアンモニア吸着量が大きいことから、
その固体酸量が多いことがわかる。また、試料3及び試
料4は、比較試料2と比べてアンモニア脱離開始温度が
高いことから、その固体酸性度も高いことがわかる。From the results in Table 2, it can be seen that Sample 3 and Sample 4 have a larger ammonia adsorption amount than Comparative Sample 2;
It turns out that the solid acid amount is large. In addition, since Sample 3 and Sample 4 have a higher ammonia desorption start temperature than Comparative Sample 2, it can be seen that the solid acidity is higher.
【図1】実施例1(1)で調製された各水酸化ジルコニ
ウムの赤外線吸収スペクトルの測定結果を示す図であ
る。FIG. 1 is a view showing a measurement result of an infrared absorption spectrum of each zirconium hydroxide prepared in Example 1 (1).
【図2】実施例1(1)で調製された各水酸化ジルコニ
ウムのX線回折測定結果を示す図である。FIG. 2 is a view showing an X-ray diffraction measurement result of each zirconium hydroxide prepared in Example 1 (1).
【図3】実施例1(2)で調製された各硫酸含有酸化ジ
ルコニウムの赤外線吸収スペクトルの測定結果を示す図
である。FIG. 3 is a view showing a measurement result of an infrared absorption spectrum of each sulfuric acid-containing zirconium oxide prepared in Example 1 (2).
【図4】実施例1(2)で調製された各硫酸含有酸化ジ
ルコニウムのX線回折測定結果を示す図である。FIG. 4 is a diagram showing an X-ray diffraction measurement result of each sulfuric acid-containing zirconium oxide prepared in Example 1 (2).
───────────────────────────────────────────────────── フロントページの続き (72)発明者 大内 公夫 大阪府大阪市住之江区平林南1丁目6番38 号 第一稀元素化学工業株式会社内 Fターム(参考) 4G048 AA02 AB05 AC08 AD04 AD06 AE05 4G069 AA01 AA05 AA08 AA09 AA12 AA14 BA45A BB05A BB05B BC51A BC51B BC59A BC60A CB62 CB75 DA05 EC03X EC03Y EC22X EC22Y FB30 FB49 FC04 FC07 FC09 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Kimio Ouchi 1- 6-38 Hirabayashiminami, Suminoe-ku, Osaka-shi, Osaka F-term (reference) 4G048 AA02 AB05 AC08 AD04 AD06 AE05 4G069 AA01 AA05 AA08 AA09 AA12 AA14 BA45A BB05A BB05B BC51A BC51B BC59A BC60A CB62 CB75 DA05 EC03X EC03Y EC22X EC22Y FB30 FB49 FC04 FC07 FC09
Claims (12)
〜1700cm-1に2以上の赤外吸収帯を有する水酸化
ジルコニウム。1. The method according to claim 1, wherein the infrared absorption spectrum is measured at 1300.
Zirconium hydroxide having two or more infrared absorption bands at 11700 cm −1 .
酸化ジルコニウムの単斜晶系に属するX線回折像を示す
請求項1記載の水酸化ジルコニウム。2. After the heat treatment at 300 to 400 ° C.,
The zirconium hydroxide according to claim 1, which shows an X-ray diffraction image belonging to a monoclinic system of zirconium oxide.
る請求項1又は2に記載の水酸化ジルコニウム。3. The zirconium hydroxide according to claim 1, having a BET specific surface area of 200 m 2 / g or more.
てスラリーを調製する第一工程、上記スラリーに塩基を
加えて水酸化物を生成させる第二工程、及び上記水酸化
物を分離回収する第三工程を有する水酸化ジルコニウム
の製造方法。4. A first step of preparing a slurry by hydrolyzing an aqueous solution of a soluble zirconium salt, a second step of adding a base to the slurry to form a hydroxide, and a third step of separating and collecting the hydroxide. A method for producing zirconium hydroxide having a step.
となるように塩基を加える請求項4記載の製造方法。5. The method according to claim 4, wherein in the second step, a base is added so that the slurry pH becomes 9 or more.
程をさらに有する請求項4又は5に記載の製造方法。6. The method according to claim 4, further comprising a fourth step of heat-treating the hydroxide at 50 ° C. or higher.
ルコニウムを硫酸、タングステン酸及びモリブデン酸の
少なくとも1種を含む水溶液で処理した後、300℃以
上で焼成することを特徴とする固体酸性組成物の製造方
法。7. The method according to claim 1, wherein the zirconium hydroxide is treated with an aqueous solution containing at least one of sulfuric acid, tungstic acid and molybdic acid, and then calcined at 300 ° C. or more. A method for producing a solid acidic composition.
成物。8. A solid acidic composition obtained by the method according to claim 7.
って、かつ、アンモニア吸着量4mmol−NH3/g
以上である請求項8記載の固体酸性組成物。9. An ammonia desorption starting temperature of 125 ° C. or higher and an ammonia adsorption amount of 4 mmol-NH 3 / g
The solid acidic composition according to claim 8, which is the above.
又は固体酸性触媒担体。10. A solid acid catalyst or a solid acidic catalyst carrier comprising the composition according to claim 9.
あって、かつ、アンモニア吸着量4mmol−NH3/
g以上であるジルコニア系固体酸性組成物。11. An ammonia desorption starting temperature of 125 ° C. or more and an ammonia adsorption amount of 4 mmol-NH 3 /
g or more, a zirconia-based solid acidic composition.
媒又は固体酸性触媒担体。12. A solid acid catalyst or a solid acidic catalyst carrier comprising the composition according to claim 11.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP05725699A JP3985116B2 (en) | 1999-03-04 | 1999-03-04 | Zirconium hydroxide and method for producing the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP05725699A JP3985116B2 (en) | 1999-03-04 | 1999-03-04 | Zirconium hydroxide and method for producing the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2000247641A true JP2000247641A (en) | 2000-09-12 |
JP3985116B2 JP3985116B2 (en) | 2007-10-03 |
Family
ID=13050460
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP05725699A Expired - Lifetime JP3985116B2 (en) | 1999-03-04 | 1999-03-04 | Zirconium hydroxide and method for producing the same |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3985116B2 (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009013029A (en) * | 2007-07-06 | 2009-01-22 | Hitachi Maxell Ltd | Zirconium oxide hydrate particles and method for producing the same |
US7794687B2 (en) | 2006-02-03 | 2010-09-14 | Magnesium Elektron Limited | Zirconium hydroxide |
WO2013008279A1 (en) | 2011-07-14 | 2013-01-17 | Nippon Kayaku Kabushiki Kaisha | Process for preparing catalyst used in production of acrolein and/or acrylic acid and process for preparing acrolein and/or acrylic acid by dehydration reaction of glycerin |
WO2014020920A1 (en) * | 2012-08-02 | 2014-02-06 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | Thermosetting silicone rubber composition |
WO2018078313A1 (en) | 2016-10-27 | 2018-05-03 | Magnesium Elektron Limited | Acidic zirconium hydroxide |
CN111439782A (en) * | 2020-03-04 | 2020-07-24 | 山西新华化工有限责任公司 | Synchronous protection NH3/SO2Preparation method of zirconium hydroxide protective material |
JP2021191728A (en) * | 2015-10-27 | 2021-12-16 | マグネシウム エレクトロン リミテッド | Acid zirconium hydroxide |
WO2023074665A1 (en) | 2021-11-01 | 2023-05-04 | 第一稀元素化学工業株式会社 | Zirconium hydroxide powder and method for producing zirconium hydroxide powder |
-
1999
- 1999-03-04 JP JP05725699A patent/JP3985116B2/en not_active Expired - Lifetime
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7794687B2 (en) | 2006-02-03 | 2010-09-14 | Magnesium Elektron Limited | Zirconium hydroxide |
JP2009013029A (en) * | 2007-07-06 | 2009-01-22 | Hitachi Maxell Ltd | Zirconium oxide hydrate particles and method for producing the same |
WO2013008279A1 (en) | 2011-07-14 | 2013-01-17 | Nippon Kayaku Kabushiki Kaisha | Process for preparing catalyst used in production of acrolein and/or acrylic acid and process for preparing acrolein and/or acrylic acid by dehydration reaction of glycerin |
CN103874736B (en) * | 2012-08-02 | 2016-11-09 | 迈图高新材料日本合同公司 | Thermocurable silicone rubber composition |
KR101998900B1 (en) | 2012-08-02 | 2019-07-10 | 모멘티브 파포만스 마테리아루즈 쟈판 고도가이샤 | Thermosetting silicone rubber composition |
US20140179870A1 (en) * | 2012-08-02 | 2014-06-26 | Momentive Performance Materials Japan Llc | Heat curable silicone rubber composition |
US8912262B2 (en) | 2012-08-02 | 2014-12-16 | Momentive Performance Materials Japan Llc | Heat curable silicone rubber composition |
KR20150040779A (en) * | 2012-08-02 | 2015-04-15 | 모멘티브 파포만스 마테리아루즈 쟈판 고도가이샤 | Thermosetting silicone rubber composition |
WO2014020920A1 (en) * | 2012-08-02 | 2014-02-06 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | Thermosetting silicone rubber composition |
CN103874736A (en) * | 2012-08-02 | 2014-06-18 | 迈图高新材料日本合同公司 | Thermosetting silicone rubber composition |
JP2021191728A (en) * | 2015-10-27 | 2021-12-16 | マグネシウム エレクトロン リミテッド | Acid zirconium hydroxide |
JP7291179B2 (en) | 2015-10-27 | 2023-06-14 | マグネシウム エレクトロン リミテッド | acid zirconium hydroxide |
US11760653B2 (en) | 2015-10-27 | 2023-09-19 | Magnesium Elektron Limited | Acidic zirconium hydroxide |
WO2018078313A1 (en) | 2016-10-27 | 2018-05-03 | Magnesium Elektron Limited | Acidic zirconium hydroxide |
CN111439782A (en) * | 2020-03-04 | 2020-07-24 | 山西新华化工有限责任公司 | Synchronous protection NH3/SO2Preparation method of zirconium hydroxide protective material |
CN111439782B (en) * | 2020-03-04 | 2022-07-29 | 山西新华防化装备研究院有限公司 | Synchronous protection NH 3 /SO 2 Preparation method of zirconium hydroxide protective material |
WO2023074665A1 (en) | 2021-11-01 | 2023-05-04 | 第一稀元素化学工業株式会社 | Zirconium hydroxide powder and method for producing zirconium hydroxide powder |
KR20240045293A (en) | 2021-11-01 | 2024-04-05 | 다이치 키겐소 카가쿠 코교 컴퍼니 리미티드 | Zirconium hydroxide powder and method for producing zirconium hydroxide powder |
Also Published As
Publication number | Publication date |
---|---|
JP3985116B2 (en) | 2007-10-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4041106B2 (en) | Composition based on cerium oxide and zirconium oxide and having high specific surface area and high oxygen storage capacity, and method for producing the same | |
JP2947449B2 (en) | Mixed oxides of cerium and zirconium, their production and use | |
CN1098811C (en) | Composite zirconium-cerium oxide, process for the preparation thereof, and cocatalyst for cleaning exhaust gas | |
US6355220B1 (en) | Method for treating exhaust gas of internal combustion engines functioning with sulphur-containing fuel | |
US20060088463A1 (en) | Process for preparing zirconium-cerium-based mixed oxides | |
AU640790B2 (en) | High surface area zirconia | |
JPS60239324A (en) | Ceric oxide with novel morphological properties and manufacture | |
CN111013614B (en) | Catalyst carrier and catalyst for preparing chlorine by oxidizing hydrogen chloride, and preparation method and application thereof | |
JP3985116B2 (en) | Zirconium hydroxide and method for producing the same | |
AU605965B2 (en) | Process for the manufacture of zirconium oxide hydrate from granular crystallized zirconium oxide | |
CN112958077B (en) | Zirconium-doped lanthanum-manganese-based SCR denitration catalyst and preparation method thereof | |
JP4972868B2 (en) | Surface-modified ceria / zirconia hydrated oxide, oxide thereof, production method thereof, and use thereof | |
CN113929058B (en) | Catalyst carrier for preparing chlorine by catalytic oxidation of fluorine-containing HCl gas, and preparation method and application thereof | |
Hasegawa et al. | Facile preparation of transparent monolithic titania gels utilizing a chelating ligand and mineral salts | |
WO2018021010A1 (en) | Method for producing glycine | |
CN100411735C (en) | Solid super acidic catalyst and its preparing method | |
JPH11292538A (en) | Production of zirconia-ceria composition | |
Patel et al. | Use of zirconium (IV) phosphate as a solid acid catalyst in some esterification reactions | |
US4111967A (en) | Silicon containing catalysts | |
CN110237836A (en) | Molybdenum modifies zirconium dioxide material and its preparation method and application | |
JP2005170775A (en) | Oxide powder, method for producing the same. and exhaust gas cleaning catalyst | |
UA125691C2 (en) | Process for reducing the sulphur content of anatase titania and the so-obtained product | |
JPH11276897A (en) | Catalyst for hydrolyzing carbonyl sulfide and hydrolysis | |
JPH01278417A (en) | Novel reactive derivative of zirconium and method for its manufacture | |
JPH0975735A (en) | Production of solid acid catalyst |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20040526 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20070626 |
|
R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100720 Year of fee payment: 3 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100720 Year of fee payment: 3 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100720 Year of fee payment: 3 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110720 Year of fee payment: 4 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110720 Year of fee payment: 4 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120720 Year of fee payment: 5 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120720 Year of fee payment: 5 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120720 Year of fee payment: 5 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130720 Year of fee payment: 6 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130720 Year of fee payment: 6 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
EXPY | Cancellation because of completion of term |