JPS62138314A - Solid acid compound and its production - Google Patents
Solid acid compound and its productionInfo
- Publication number
- JPS62138314A JPS62138314A JP60277737A JP27773785A JPS62138314A JP S62138314 A JPS62138314 A JP S62138314A JP 60277737 A JP60277737 A JP 60277737A JP 27773785 A JP27773785 A JP 27773785A JP S62138314 A JPS62138314 A JP S62138314A
- Authority
- JP
- Japan
- Prior art keywords
- zirconium phosphate
- sulfuric acid
- compd
- acid
- rays
- 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
- 239000011973 solid acid Substances 0.000 title claims abstract description 16
- 150000001875 compounds Chemical class 0.000 title claims description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims abstract description 20
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000000634 powder X-ray diffraction Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 16
- 235000011149 sulphuric acid Nutrition 0.000 abstract description 5
- 239000000843 powder Substances 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 11
- 229910019142 PO4 Inorganic materials 0.000 description 8
- 235000021317 phosphate Nutrition 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- -1 montmorillonite Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- 101100283604 Caenorhabditis elegans pigk-1 gene Proteins 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000001261 hydroxy acids Chemical class 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052680 mordenite 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
- 229940085991 phosphate ion Drugs 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Conductive Materials (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
木兄ＢＡは、リン酸ジルコニウムと硫酸との反応によつ
て得られる固体酸化合物およびその製造方法に関するも
のである。DETAILED DESCRIPTION OF THE INVENTION Kinoe BA relates to a solid acid compound obtained by the reaction of zirconium phosphate and sulfuric acid, and a method for producing the same.
産業上の利用分野
本発明の化合物は、リン酸ジルコニウムと硫酸の反応に
よって得られ、結晶内に硫酸を含む固体酸である。した
がって、この化合物は触媒、イオン交換体、イオン導電
体、吸着剤などとしての利用およびそれらの製造原料と
して利用することができる。また、結晶内に固定化され
た仙Ｃ酸は４００〜５００℃で脱離する性質を利用して
、高温でのみ硫酸を与える素材としての利用も開発され
よう。Industrial Application Field The compound of the present invention is a solid acid obtained by the reaction of zirconium phosphate and sulfuric acid, and contains sulfuric acid in its crystals. Therefore, this compound can be used as a catalyst, ion exchanger, ion conductor, adsorbent, etc., and as a raw material for their production. Furthermore, by taking advantage of the property that SAC acid fixed in crystals is desorbed at 400 to 500°C, it will be possible to develop its use as a material that provides sulfuric acid only at high temperatures.
従来の技術
これまで、多くの固体酸が知られている。たとえば、ア
ルミナやシリカアルミナなど多くの金属酸化物および複
合酸化物、モルデナイトなどのゼオライト、モンモリロ
ナイトなどの天然層状ケイ酸塩、ヘテロポリ酸およびリ
ン酸塩などがある。BACKGROUND OF THE INVENTION Many solid acids are known to date. Examples include many metal oxides and composite oxides such as alumina and silica-alumina, zeolites such as mordenite, natural layered silicates such as montmorillonite, heteropolyacids and phosphates.
さらにイオウの酸化物を含む固体酸としては、たとえば
ペルフルオロスルホン酸樹脂などのスルホン酸型イオン
交換樹脂がある。これらは耐熱性の理由から通常２００
Ｃ以下で使用される。また、最近ＴｉＯ、ＺｒＯ２、Ｆ
ｅ２Ｏ３にＳｏ４ を担持した固体戯が開発さｎｆｃ
（先出ら１表面１９ 、７５（１９８１））、。Furthermore, solid acids containing sulfur oxides include, for example, sulfonic acid type ion exchange resins such as perfluorosulfonic acid resins. These are usually 200% for heat resistance reasons.
Used below C. In addition, recently TiO, ZrO2, F
A solid material carrying So4 on e2O3 was developed as NFC.
(Suede et al. 1, 1997, 75 (1981)).
この固体酸は、無水条件下では５５０〜６００℃での焼
成にも耐えるが、水または水蒸気の存在下ではＳ０４
が脱離すると言われる。、ざらにまた、グラファイト
を陰極として９８チ硫酸を電解して層間化合物Ｃ２４＋
Ｈ３Ｏ４−・２Ｈ２ＳＯ４が合成された（ Ｈ，Ｂ、
Ｋａｇａｎら、 Ｊ、 Ａｍ、Ｃｈｅｍ、 Ｓｏｃ、
、 ９６ ｒ８１１３（１９７４））。この固体酸は、
エステル化触媒として高活性を示すが、加水分解によっ
てグラファイトオキシドに変化しやすい欠点を有すると
言われる。最近、ｚｒＰ２ｏ７またＦｉＺ ｒ ２ Ｐ
２０９を旋硫酸中で数日間煮沸することによって、結
晶骨格中にＳ０４基を含むＺｒ２ （ＰＯ４）２ （Ｓ
Ｏ４）が合ｇされた（ Ｒ，Ｒｏｙら、 Ｊ、 ５ｏｌ
ｉｄ ５ｔａｔｅ Ｃｈｅｍ、 、 ５１ ｅ２７０（
１９８４））。この固体酸化合物のα−型結晶は、７５
０℃まで安定でちゃ、それよシ高温ではｓｏ、を脱離し
てα−Ｚ ｒ ２ Ｐ ２０ ｐになる。また、β−型
結晶は、１０００℃から同様に分解する。これらの化合
物は、リン酸塩と硫酸塩から成る蝮リン酸塩であり、Ｓ
０４基は結晶の骨格を形成しているものであって、前記
のグラファイトと硫酸の付加物のよりに層間あるいは結
晶内のトンネル中などに存在する硫酸（根）ではない。This solid acid can withstand calcinations at 550-600°C under anhydrous conditions, but in the presence of water or steam it can withstand S04
is said to be leaving. , Zarani also electrolyzed 98-thiosulfuric acid using graphite as a cathode to form an intercalation compound C24+.
H3O4-・2H2SO4 was synthesized (H, B,
Kagan et al., J. Am. Chem. Soc.
, 96 r8113 (1974)). This solid acid is
Although it exhibits high activity as an esterification catalyst, it is said to have the disadvantage of being easily converted to graphite oxide by hydrolysis. Recently, zrP2o7 also FiZ r 2 P
By boiling 209 in sulfuric acid for several days, Zr2 (PO4)2 (S
O4) was combined (R, Roy et al., J, 5ol
id 5tate Chem, , 51 e270(
1984)). The α-type crystal of this solid acid compound is 75
It should be stable down to 0°C, but at high temperatures, so is eliminated and becomes α-Z r 2 P 20 p. Further, β-type crystals similarly decompose from 1000°C. These compounds are phosphoric acid salts consisting of phosphate and sulfate; S
The 04 group forms the skeleton of the crystal, and is not the sulfuric acid (root) that exists between layers or in tunnels within the crystal due to the addition of graphite and sulfuric acid.
発Ｅ！Ａが解決しようとする問題点
前記の公知化合物は、固体酸としての性質を有するもの
であるが、それらのうち硫酸のようなブレンステッド酸
性を示す固体酸は、熱や水に弱すものが多い。Release E! Problem A aims to solve The above-mentioned known compounds have properties as solid acids, but among them, solid acids that exhibit Brønsted acidity, such as sulfuric acid, are sensitive to heat and water. many.
問題点を解決するための手段
本発明者は、安定な固体のブレンステッド酸を開発する
目的で、リン酸塩の研究を行った結果、リン酸ジルコニ
ウムと硫酸の反応生成物が、その目的に適合しうる化合
物であることを見出し、本発明を完成した。Means for Solving the Problems The present inventor conducted research on phosphates for the purpose of developing a stable solid Brønsted acid, and found that the reaction product of zirconium phosphate and sulfuric acid could be used for that purpose. The present invention was completed by discovering that the compound is compatible with the present invention.
本発明に従ってリン酸ジルコニウムと硫酸の反応によっ
て得られる化合物であって、ＣｕＫ、Ｘ線による粉末Ｘ
線回折図形の２０が５°〜５０’の範囲において次の位
置に回折線を有する化合物が提供される。例えば、実施
例１で得られた化合物にっ込ての、相対強度百分率（Ｉ
／Ｉ、）は
２θ’ １４．２２，１５．６７．１９．９８，２０
．９８，２２．２４，２３．３２Ｉ／Ｉ、 ２５
９ ６９ １ ６ 膳ｈ２θ’ ２３．７
０，２４．４５．２５．７０，２６．４６，２８．２３
，２８．７７１／Ｔ、 ６７ １ ２０ １１
１４ １００２θ’ ２９．１６，３１．０７
，３１．７４，３２．１４，３２．３６，３５．１８Ｉ
／Ｉ、 ３ ３ １ ９ ６ １９２θ
’ ４０．７７．４５．５０，４６．２４．４６．５
８，４８．５４，４９．７３Ｉ／Ｉ、 ３ ４
４２ ５ ５ ４である。このＩ／ＩｏＦｉ図
形中の最図形−回折線を標準とした相対強度百分率であ
り、２θが１４．２２°。A compound obtained according to the invention by the reaction of zirconium phosphate and sulfuric acid, comprising CuK, powder X by X-rays.
A compound having a diffraction line at the following position in the range of 5° to 50' in the line diffraction pattern is provided. For example, the relative intensity percentage (I
/I,) is 2θ' 14.22, 15.67.19.98, 20
．． 98, 22.24, 23.32I/I, 25
9 69 1 6 Zen h2θ' 23.7
0, 24.45.25.70, 26.46, 28.23
,28.771/T, 67 1 20 11
14 1002θ' 29.16, 31.07
, 31.74, 32.14, 32.36, 35.18I
/I, 3 3 1 9 6 192θ
' 40.77.45.50, 46.24.46.5
8,48.54,49.73I/I, 3 4
42 5 5 4. This is the relative intensity percentage based on the maximum figure-diffraction line in this I/IoFi figure, and 2θ is 14.22°.
１９．９８°、２３゜７０°、２８．７７°および４６
．２４°の位置で特徴的である。この数値は結晶化度に
よって変化するので絶対的なものではない。19.98°, 23°70°, 28.77° and 46
．． It is characteristic at the 24° position. This value is not absolute because it changes depending on the degree of crystallinity.
この化合物の詳細な結晶構造は未だ不明であるが、その
Ｘ線回折図形はナシコン型結晶の特徴を示し、トンネル
構造を持つものと考えられる。また、この化合物の赤外
吸収ス被りトルｈｐ−ｏ結合およびＳ−０結合の存在を
示す。さらに、この化合物の熱天秤測定結果は、４００
〜５．００１：において硫酸（Ｓｏ、 ＋ Ｈ２Ｏ）の
脱離および１２００’Ｃ以上においてＳ０３の脱離によ
る減量を示し、２種類の８０４基が存在することを示す
。この化合物のＸ線回折、熱天秤による分析結果は、公
知のｚｒ２（ｐｏ４） ２ （Ｓｏ４）のものと異って
おり、本発明の化合物におけるＳ０４基は複リン酸塩の
結晶を形成するもの＜ １２００℃脱離）と結晶内にイ
ンターカレート（または固定）されたＨ２ＳＯ４（４０
０〜５００℃脱離）に基づくものの２ ａｔ類であると
考えられる。Although the detailed crystal structure of this compound is still unknown, its X-ray diffraction pattern shows characteristics of a Nasicon-type crystal, and it is thought to have a tunnel structure. The infrared absorption spectrum of this compound also indicates the presence of hp-o and S-0 bonds. Furthermore, the thermobalance measurement result of this compound is 400
~5.001: shows a weight loss due to elimination of sulfuric acid (So, + H2O) and at 1200'C or higher due to elimination of S03, indicating the existence of two types of 804 groups. The analysis results of this compound by X-ray diffraction and thermal balance are different from those of known zr2(po4) 2 (So4), and the S04 group in the compound of the present invention forms a crystal of a double phosphate. < 1200 °C desorption) and H2SO4 intercalated (or fixed) within the crystal (40
It is thought that it is a 2 at type based on the desorption at 0 to 500°C.
本発明の化合物は、リン酸ジルコニウムを硫酸中で加熱
して製造される。原料として用いられるリン酸ジルコニ
ウムは、無定形のものでも結晶性のものでもよい。好ま
しくは、層状構造を有するリン酸ジルコニウムたとえば
Ｚｒ （ＨＰＯ４） ２・ｎＨ２０（ｎ；０〜２）など
が用いられる。これらのウチ、結晶性のものの例として
は、α、β、γ、δ、ε。The compounds of the present invention are produced by heating zirconium phosphate in sulfuric acid. Zirconium phosphate used as a raw material may be amorphous or crystalline. Preferably, zirconium phosphate having a layered structure, such as Zr (HPO4) 2.nH20 (n; 0 to 2), is used. Examples of these crystalline substances are α, β, γ, δ, and ε.
ζ、ηなどの結晶形のリン酸ジルコニウムがあげらｔし
る。さらに好ましくは、β、γおよびとくにε型のリン
酸ジルコニウムが用いられる。一方、ｚｒＰ２０７やＺ
ｒ ２Ｐ ２０ ｑなどの縮合リン酸塩なども用いる
ことはできるが、必すしも好適な原料ではない。Examples include crystalline forms of zirconium phosphate such as ζ and η. More preferably, zirconium phosphates of the β, γ and especially ε types are used. On the other hand, zrP207 and Z
Condensed phosphates such as r 2 P 20 q can also be used, but are not necessarily suitable raw materials.
また、用いられる侃酸は縫硫酸が好ましい。好適な反応
温度は反応時間（一般には数時間から数ケ月であるが、
通常数日から数週間）によっても異るが一般に、７０〜
３００℃、好ましくは１２０〜２５０℃、さらに好筐し
くは１５０〜２２０℃である。このようにして得られる
反応混合物から目的化合物を単離するには、生成し次結
晶を母液から口過などによって分離し、洗浄後乾燥する
。Further, the hydroxy acid used is preferably sulfuric acid. The suitable reaction temperature is the reaction time (generally several hours to several months, but
Generally, 70~
The temperature is 300°C, preferably 120-250°C, more preferably 150-220°C. In order to isolate the target compound from the reaction mixture thus obtained, the formed crystals are separated from the mother liquor by filtration or the like, washed, and then dried.
目的化合物は、その粉末Ｘ線回折図形が前記の特徴を示
すので、これによって固定することができる。The target compound can be immobilized because its powder X-ray diffraction pattern exhibits the above-mentioned characteristics.
作用および発明の効果
本発明の化合物は、その結晶内にＨ２ＳＯ４を固定化し
て保有しており、４００〜５００℃でこの硫酸を脱離す
る性質を有するので、耐熱性の固定化硫酸として触媒、
イオン交換体などや、高温で硫酸を与える素材として好
適に利用される。Actions and Effects of the Invention The compound of the present invention has H2SO4 fixed in its crystals and has the property of desorbing this sulfuric acid at 400 to 500°C. Therefore, it can be used as a heat-resistant immobilized sulfuric acid as a catalyst.
It is suitable for use as an ion exchanger or as a material that provides sulfuric acid at high temperatures.
実施例 実施例によって本発明をさらに詳細に説明する。Example The present invention will be explained in more detail by way of examples.
実施例１
硝酸ジルコニル（ＺｒＯ（Ｎｏ ） ・２ Ｈ２Ｏ）
ＡＣ溶液をりン酸中に滴下することによって生成した無
定形リン酸ジルコニウムを乾燥後、濃リン酸中、減圧下
で１８０℃まで加熱した。生じた結晶を母液から分離し
、洗浄後乾燥してε−リン酸ゾルコニウムを得た。Example 1 Zirconyl nitrate (ZrO(No) 2 H2O)
The amorphous zirconium phosphate produced by dropping the AC solution into phosphoric acid was dried and then heated to 180° C. under reduced pressure in concentrated phosphoric acid. The resulting crystals were separated from the mother liquor, washed and dried to obtain ε-zolconium phosphate.
ε−リン酸ジルコニウムＩＯＮをＤａ酸１００ｄ中に加
え、１６０℃で７日間加熱後、結晶を母液から分離し、
洗浄後乾燥した。このようにして得られた結晶の分析値
は次のとおり： Ｚ ｒ Ｏ２４８，３６チ、Ｐ２Ｏ５
４１，４７％、Ｈ２ＳＯ４１０，１７％また粉末Ｘ線回
折図形は第１図に示すとおり本発明の化合物の特徴を全
て有していた。ε-zirconium phosphate ION was added to 100 d of Da acid, and after heating at 160°C for 7 days, the crystals were separated from the mother liquor,
After washing, it was dried. The analytical values of the crystals thus obtained are as follows: Z r O248,36, P2O5
41.47%, H2SO4 10.17%.The powder X-ray diffraction pattern had all the characteristics of the compound of the present invention as shown in FIG.
更に、この化合物の熱天秤測定結果を第２図に示す。測
定は空気中、昇温速度１０°／ ｍ ｉ ｎで行われた
。Furthermore, the results of thermobalance measurements of this compound are shown in FIG. Measurements were performed in air at a heating rate of 10°/min.
実施例２
実施例１で合成した本発明の化合物を空気中、５００℃
で焼成したものを触媒として利用した例を示す。内容ｙ
２４０ｍｌｔ：ｒｈ閉塞循環反応装置に、この触媒２０
０ｍ９とシス−２−ブテン７０址ｇを仕込み、反応温度
４０℃でシス−２−ブテンの異性化反応を行った結果を
表１に示す。Ｔ／１は生成したトランス−２−ブテンと
１−２テンの生成比を表わし、活性は、触媒の単位表面
積当シの相対活性（比較例ａおよびｂとの比較）を示す
。Example 2 The compound of the present invention synthesized in Example 1 was heated at 500°C in air.
An example of using the calcined product as a catalyst is shown below. Contents
240 mlt: rh closed circulation reactor, this catalyst 20
Table 1 shows the results of an isomerization reaction of cis-2-butene at a reaction temperature of 40°C. T/1 represents the production ratio of trans-2-butene and 1-2-tene, and activity represents the relative activity per unit surface area of the catalyst (comparison with Comparative Examples a and b).
比較例ａおよびｂ
実施例２において、触媒として５００℃で焼成したε−
リン酸ゾルコニウム（比較例ａ）およびＳｉＯ・Ａｔ２
０３（比較例ｂ）を用いた以外は全て同様に実施した。Comparative Examples a and b In Example 2, ε- calcined at 500°C was used as a catalyst.
Zorconium phosphate (comparative example a) and SiO.At2
All experiments were carried out in the same manner except that 03 (Comparative Example b) was used.
結果を表１に示す。The results are shown in Table 1.
表 １
固体酸触媒では、Ｔ／１は触媒の酸強度が大きいほど大
きくなることが知られている。したがって、実施例２の
触媒ｖｌ値が大きいことよシ、これらのうちでは酸強度
が最も大きいことを示している。Table 1 It is known that in solid acid catalysts, T/1 increases as the acid strength of the catalyst increases. Therefore, the fact that the catalyst vl value of Example 2 is large indicates that the acid strength is the highest among these catalysts.
第１図は本発明の化合物の粉末Ｘ線回折図形を示し、第
２図は熱天秤測定結果を示すグラフである。FIG. 1 shows a powder X-ray diffraction pattern of the compound of the present invention, and FIG. 2 is a graph showing the results of thermobalance measurement.
Claims (1)
る化合物でありて、ＣｕＫ＿αＸ線による粉末Ｘ線回折
図形において、２θが１４．２２°、１９．９８°、２
３．７０°、２８．７７°および４６．２４°の位置に
特徴的な主たる回折線を有する固体酸化合物。 ２）リン酸ジルコニウムが層状構造を有するリン酸ジル
コニウムであることを特徴とする特許請求の範囲第１項
記載の固体酸化合物。 ３）リン酸ジルコニウムを濃硫酸中で加熱することを特
徴とする特許請求の範囲第１項記載の固体酸化合物の製
造方法。 ４）リン酸ジルコニウムが層状構造を有するリン酸ジル
コニウムであることを特徴とする特許請求の範囲第３項
記載の製造方法。 ５）加熱温度が７０〜３００℃である特許請求の範囲第
２項記載の方法。[Scope of Claims] 1) A compound obtained by the reaction of zirconium phosphate and sulfuric acid, which has a powder X-ray diffraction pattern using CuK_α X-rays with 2θ of 14.22°, 19.98°, 2
A solid acid compound with characteristic main diffraction lines at 3.70°, 28.77° and 46.24°. 2) The solid acid compound according to claim 1, wherein the zirconium phosphate is a zirconium phosphate having a layered structure. 3) The method for producing a solid acid compound according to claim 1, which comprises heating zirconium phosphate in concentrated sulfuric acid. 4) The manufacturing method according to claim 3, wherein the zirconium phosphate is a zirconium phosphate having a layered structure. 5) The method according to claim 2, wherein the heating temperature is 70 to 300°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60277737A JPH0742094B2 (en) | 1985-12-10 | 1985-12-10 | Solid acid compound and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60277737A JPH0742094B2 (en) | 1985-12-10 | 1985-12-10 | Solid acid compound and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62138314A true JPS62138314A (en) | 1987-06-22 |
| JPH0742094B2 JPH0742094B2 (en) | 1995-05-10 |
Family
ID=17587620
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60277737A Expired - Lifetime JPH0742094B2 (en) | 1985-12-10 | 1985-12-10 | Solid acid compound and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0742094B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003060925A1 (en) * | 2002-01-16 | 2003-07-24 | Nagoya Industrial Science Research Institute | Proton-conductive gel, proton conductor, and processes for producing these |
| KR100803057B1 (en) | 2006-11-03 | 2008-02-18 | 한국과학기술연구원 | Methanol decomposition catalyst based on solid acid materials and method for preparing the same |
| WO2019167924A1 (en) * | 2018-02-27 | 2019-09-06 | 国立大学法人東京工業大学 | Negative thermal expansion material, composite material, and method for producing negative thermal expansion material |
| WO2021261049A1 (en) * | 2020-06-22 | 2021-12-30 | 三井金属鉱業株式会社 | Compound, production method therefor, and composite material |
-
1985
- 1985-12-10 JP JP60277737A patent/JPH0742094B2/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003060925A1 (en) * | 2002-01-16 | 2003-07-24 | Nagoya Industrial Science Research Institute | Proton-conductive gel, proton conductor, and processes for producing these |
| KR100803057B1 (en) | 2006-11-03 | 2008-02-18 | 한국과학기술연구원 | Methanol decomposition catalyst based on solid acid materials and method for preparing the same |
| WO2019167924A1 (en) * | 2018-02-27 | 2019-09-06 | 国立大学法人東京工業大学 | Negative thermal expansion material, composite material, and method for producing negative thermal expansion material |
| KR20200125634A (en) * | 2018-02-27 | 2020-11-04 | 고쿠리츠다이가쿠호진 토쿄고교 다이가꾸 | Subthermal expansion material, composite material, and method of manufacturing subthermal expansion material |
| WO2021261049A1 (en) * | 2020-06-22 | 2021-12-30 | 三井金属鉱業株式会社 | Compound, production method therefor, and composite material |
| JP7029576B1 (en) * | 2020-06-22 | 2022-03-03 | 三井金属鉱業株式会社 | Compounds, their manufacturing methods, and composite materials |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0742094B2 (en) | 1995-05-10 |
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